JPWO2017111143A1 - Non-aqueous electrolyte battery electrolyte and non-aqueous electrolyte battery using the same - Google Patents

Abstract

［１］

When used in a non-aqueous electrolyte battery, an electrolyte solution for a non-aqueous electrolyte battery that can exert a good balance between the effect of suppressing an increase in internal resistance at low temperatures and the effect of suppressing the amount of gas generated at high temperatures, and The used non-aqueous electrolyte battery is provided. The nonaqueous electrolytic solution includes a nonaqueous solvent and a solute. It contains at least hexafluorophosphate and / or tetrafluoroborate as a solute, at least one salt having an imide anion represented by the following general formula [1], and represented by the following general formula [2]. In addition, for example, it does not contain an ionic complex represented by the following general formula [3].

[1]

Description

The present invention is a non-aqueous electrolyte battery that can exert a good balance between the effect of suppressing an increase in internal resistance at low temperatures and the effect of suppressing the amount of gas generated at high temperatures when used in a non-aqueous electrolyte battery. The present invention relates to an electrolytic solution and a nonaqueous electrolytic battery using the same.

In recent years, power storage systems, electric vehicles, hybrid vehicles, and fuel cells for information-related devices or communication devices, that is, small devices such as personal computers, video cameras, digital still cameras, mobile phones, and the like that require high energy density Energy storage systems are attracting attention for large-scale equipment such as car auxiliary power supplies and power storage, and for applications that require power. Non-aqueous electrolyte batteries such as lithium ion batteries, lithium batteries, lithium ion capacitors, and sodium ion batteries have been actively developed as one candidate.

Although many of these non-aqueous electrolyte batteries have already been put into practical use, they are not satisfactory for various uses in each characteristic. Especially for in-vehicle applications such as electric vehicles, high input / output characteristics are required even in cold periods, so it is important to improve low-temperature characteristics, and even when repeatedly charged and discharged in a high-temperature environment. Is required (high increase in internal resistance). In addition, in order to reduce the weight of the battery, a laminate type battery using a laminate film such as an aluminum laminate film is often used as an exterior member, but these batteries are deformed due to expansion or the like due to gas generation inside the battery. There is a problem that it is easy.

As a means to improve battery characteristics (cycle characteristics) when high-temperature characteristics and charge / discharge of non-aqueous electrolyte batteries are repeated, optimization of various battery components including positive and negative electrode active materials has been studied. It has been. Non-aqueous electrolyte-related technology is no exception, and it has been proposed to suppress degradation due to decomposition of the electrolyte on the surface of an active positive electrode or negative electrode with various additives. For example, Patent Document 1 proposes to improve battery characteristics by adding vinylene carbonate to an electrolytic solution. However, although the battery characteristics at high temperature are improved, the increase in internal resistance is remarkably deteriorated at low temperature. Many studies have also been made on adding an imide salt to an electrolytic solution. For example, a method of suppressing deterioration of high-temperature cycle characteristics and high-temperature storage characteristics by combining a specific sulfonimide salt or phosphorylimide salt with an oxalato complex. (Patent Document 2), a method of suppressing deterioration of cycle characteristics and output characteristics by combining a specific sulfonimide salt and a fluorophosphate (Patent Document 3) and the like have been proposed.

JP 2000-123867 A JP2013-051212A JP2013-030465A

  The low-temperature characteristics and high-temperature storage characteristics obtained by the non-aqueous electrolyte battery using the non-aqueous electrolyte disclosed in the prior art document are not fully satisfactory and have room for improvement. For example, in more severe applications, an electrolyte for a non-aqueous electrolyte battery that can suppress an increase in internal resistance at a low temperature of −30 ° C. or lower, or a gas generation amount at a high temperature of 70 ° C. or higher. There is a need for non-aqueous electrolyte batteries using the same.

The present invention, when used in a non-aqueous electrolyte battery, is capable of exerting a good balance between the effect of suppressing an increase in internal resistance at low temperatures and the effect of suppressing the amount of gas generated at high temperatures. An object is to provide an electrolytic solution and a non-aqueous electrolytic battery using the electrolytic solution.

As a result of intensive studies in view of such problems, the present inventors have determined that at least hexafluorophosphate and / or tetrafluoroboric acid as a solute in a nonaqueous electrolyte solution for a nonaqueous electrolyte battery containing a nonaqueous solvent and a solute. When the electrolyte is used in a non-aqueous electrolyte battery by containing a salt and having a imide anion having a specific structure in the electrolyte, the non-aqueous electrolyte battery has an internal resistance at a low temperature. The present inventors have found that the effect of suppressing the increase in gas and the effect of suppressing the amount of gas generated at a high temperature can be exhibited in a well-balanced manner.

［１］

［一般式［１］中、Ｒ¹〜Ｒ³ は、それぞれ互いに独立して、フッ素原子、炭素数が１〜１０の直鎖あるいは分岐状のアルキル基、炭素数が１〜１０の直鎖あるいは分岐状のアルコキシ基、炭素数が２〜１０のアルケニル基、炭素数が２〜１０のアルケニルオキシ基、炭素数が２〜１０のアルキニル基、炭素数が２〜１０のアルキニルオキシ基、炭素数が３〜１０のシクロアルキル基、炭素数が３〜１０のシクロアルコキシ基、炭素数が３〜１０のシクロアルケニル基、炭素数が３〜１０のシクロアルケニルオキシ基、炭素数が６〜１０のアリール基、及び、炭素数が６〜１０のアリールオキシ基から選ばれる有機基であり、その有機基中にフッ素原子、酸素原子、不飽和結合が存在することもできる。但し、Ｒ¹〜Ｒ³の少なくとも１つはフッ素原子である。Ｍ^m+は、アルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンであり、ｍは、該当するカチオンの価数と同数の整数を表す。］
Ｓｉ（Ｒ⁴）_a（Ｒ⁵）_4-a ［２］
［一般式［２］中、Ｒ⁴は、それぞれ互いに独立して炭素−炭素不飽和結合を有する基を表す。Ｒ⁵は、それぞれ互いに独立して炭素数が１〜１０の直鎖あるいは分岐状のアルキル基を示し、これらの基は、フッ素原子及び／又は酸素原子を有していても良い。aは、２〜４の整数である。］In addition, the applicant of the present invention has an excellent low-temperature output characteristic and can exhibit excellent cycle characteristics and storage characteristics at high temperatures, and a non-aqueous electrolysis using the same. The invention relating to the liquid battery has been filed as Japanese Patent Application No. 2015-030411. In the Japanese Patent Application No. 2015-030411, an electrolyte solution for a non-aqueous electrolyte battery containing a salt having an imide anion represented by the following general formula [1] and a silane compound represented by the following general formula [2] Is also described.

[1]

[In General Formula [1], R ^{1 to} R ³ are each independently a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 1 to 10 carbon atoms, or Branched alkoxy group, alkenyl group having 2 to 10 carbon atoms, alkenyloxy group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkynyloxy group having 2 to 10 carbon atoms, carbon number Is a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. An organic group selected from an aryl group and an aryloxy group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, and an unsaturated bond may be present in the organic group. However, at least one of R ^{1 to} R ³ is a fluorine atom. M ^{m +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. ]
Si (R ⁴ ) _a (R ⁵ ) _4-a [2]
[In the general formula [2], R ⁴ each independently represents a group having a carbon-carbon unsaturated bond. R ⁵ represents each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and these groups may have a fluorine atom and / or an oxygen atom. a is an integer of 2-4. ]

［１］

［一般式［１］において、
Ｒ¹〜Ｒ³ は、それぞれ互いに独立して、フッ素原子、炭素数が１〜１０の直鎖あるいは分岐状のアルキル基、炭素数が１〜１０の直鎖あるいは分岐状のアルコキシ基、炭素数が２〜１０のアルケニル基、炭素数が２〜１０のアルケニルオキシ基、炭素数が２〜１０のアルキニル基、炭素数が２〜１０のアルキニルオキシ基、炭素数が３〜１０のシクロアルキル基、炭素数が３〜１０のシクロアルコキシ基、炭素数が３〜１０のシクロアルケニル基、炭素数が３〜１０のシクロアルケニルオキシ基、炭素数が６〜１０のアリール基、及び、炭素数が６〜１０のアリールオキシ基から選ばれる有機基であり、その有機基中にフッ素原子、酸素原子、不飽和結合が存在することもできる。
但し、Ｒ¹〜Ｒ³の少なくとも１つは、フッ素原子である。Ｍ^m+は、アルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンであり、ｍは、該当するカチオンの価数と同数の整数を表す。］

［一般式［３］において、
Ａ^b+は、金属イオン、プロトン及びオニウムイオンからなる群から選ばれる少なくとも１つであり、
Ｆは、フッ素原子であり、
Ｍは、１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれる少なくとも１つであり、
Ｏは、酸素原子であり、
Ｓは、硫黄原子である。
Ｒ⁶は、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ⁷）−を表す。このとき、Ｒ⁷は水素原子、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ⁷は分岐鎖あるいは環状構造をとることもできる。
Ｙは、炭素原子又は硫黄原子である。Ｙが炭素原子である場合、ｒは１である。Ｙが硫黄原子である場合、ｒは１又は２である。
ｂは、１又は２、ｏは２又は４、ｎは、１又は２、ｐは、０又は１、ｑは、１又は２、ｒは、０、１又は２である。ｐが、０の場合、Ｓ−Ｙ間に直接結合を形成する。］

［一般式［４］において、
Ａ^b+は、金属イオン、プロトン及びオニウムイオンからなる群から選ばれる少なくとも１つであり、
Ｆは、フッ素原子であり、
Ｍは、１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれる少なくとも１つであり、
Ｏは、酸素原子であり、
Ｎは、窒素原子である。
Ｙは、炭素原子又は硫黄原子であり、Ｙが炭素原子である場合、ｑは、１であり、Ｙが硫黄原子である場合、ｑは、１又は２である。
Ｒ⁶は、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ⁷）−を表す。このとき、Ｒ⁷は、水素原子、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ⁷は、分岐鎖あるいは環状構造をとることもできる。
Ｒ⁸は、水素原子、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ⁷）−を表す。このとき、Ｒ⁷は、水素原子、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ⁷は、分岐鎖あるいは環状構造をとることもできる。
ｂは、１又は２、ｏは、２又は４、ｎは、１又は２、ｐは、０又は１、ｑは、１又は２、ｒは、０又は１である。ｐが０の場合、Ｒ⁶の両隣に位置する原子同士（すなわち、Ｙと炭素原子）が直接結合を形成する。ｒが０の場合Ｍ−Ｎ間に直接結合を形成する。］

［一般式［５］において、
Ｄは、ハロゲンイオン、ヘキサフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ビス（トリフルオロメタンスルホニル）イミドアニオン、ビス（フルオロスルホニル）イミドアニオン、（フルオロスルホニル）（トリフルオロメタンスルホニル）イミドアニオン、ビス（ジフルオロホスホニル）イミドアニオンから選ばれる少なくとも一つであり、
Ｆは、フッ素原子であり、
Ｍは、１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれるいずれか１つであり
Ｏは、酸素原子であり、
Ｎは、窒素原子である。
Ｙは、炭素原子又は硫黄原子であり、Ｙが炭素原子である場合、ｑは、１であり、Ｙが硫黄原子である場合、ｑは、１又は２である。
Ｘは、炭素原子又は硫黄原子であり、Ｘが炭素原子である場合、ｒは、１であり、Ｘが硫黄原子である場合、ｒは、１又は２である。
Ｒ⁶は、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ⁷）−を表す。このとき、Ｒ⁷は、水素原子、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ⁷は、分岐鎖あるいは環状構造をとることもできる。
Ｒ⁹、Ｒ¹⁰は、それぞれ独立で炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。また、下記一般式［６］の様にお互いを含む環状構造を有しても良い。

ｃは、０又は１であり、ｎが１の場合、ｃは、０（ｃが０のとき、Ｄは存在しない）であり、ｎが２の場合、ｃは、１となる。
ｏは、２又は４、ｎは、１又は２、ｐは、０又は１、ｑは、１又は２、ｒは、１又は２、ｓは、０又は１である。ｐが０の場合、Ｙ−Ｘ間に直接結合を形成する。
ｓが０の場合、Ｎ（Ｒ⁹）（Ｒ¹⁰）とＲ⁶は直接結合し、その際、下記の［７］〜［１０］のような構造をとることもできる。直接結合が二重結合となる［８］及び［１０］の場合、Ｒ¹⁰は、存在しない。また［９］の様に二重結合が環の外に出た構造を取ることも出来る。この場合のＲ¹¹及びＲ¹²は、それぞれ独立で水素原子、又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。）

In addition, the applicant of the present application has made Japanese Patent Application No. 2015 regarding an electrolyte for a non-aqueous electrolyte battery containing a material suitable for a non-aqueous electrolyte battery having high-temperature durability and a non-aqueous electrolyte battery using the same. Filed as -130613. The Japanese Patent Application No. 2015-130613 contains a salt having an imide anion represented by the following general formula [1] and at least one ionic complex represented by the following general formulas [3] to [5]. It also describes an electrolyte for a water electrolyte battery.

[1]

[In general formula [1],
R ^{1 to} R ³ are each independently a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a carbon number Is an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. A cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number It is an organic group selected from 6 to 10 aryloxy groups, and fluorine atoms, oxygen atoms, and unsaturated bonds may be present in the organic groups.
However, at least one of R ^{1 to} R ³ is a fluorine atom. M ^{m +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. ]

[In general formula [3],
A ^{b +} is at least one selected from the group consisting of metal ions, protons and onium ions,
F is a fluorine atom,
M is at least one selected from the group consisting of a group 13 element (Al, B), a group 14 element (Si), and a group 15 element (P, As, Sb);
O is an oxygen atom,
S is a sulfur atom.
R ⁶ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can also be used. ), or -N (R ⁷⁾ - represents a. At this time, R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can take a branched chain or a cyclic structure.
Y is a carbon atom or a sulfur atom. When Y is a carbon atom, r is 1. When Y is a sulfur atom, r is 1 or 2.
b is 1 or 2, o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, and r is 0, 1 or 2. When p is 0, a direct bond is formed between S and Y. ]

[In the general formula [4]
A ^{b +} is at least one selected from the group consisting of metal ions, protons and onium ions,
F is a fluorine atom,
M is at least one selected from the group consisting of a group 13 element (Al, B), a group 14 element (Si), and a group 15 element (P, As, Sb);
O is an oxygen atom,
N is a nitrogen atom.
Y is a carbon atom or a sulfur atom, q is 1 when Y is a carbon atom, and q is 1 or 2 when Y is a sulfur atom.
R ⁶ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can also be used. ), or -N (R ⁷⁾ - represents a. At this time, R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can take a branched chain or a cyclic structure.
R ⁸ represents a hydrogen atom, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, it has a branched chain or cyclic structure). Or -N (R ⁷ )-. At this time, R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can take a branched chain or a cyclic structure.
b is 1 or 2, o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, and r is 0 or 1. When p is 0, atoms located on both sides of R ⁶ (that is, Y and a carbon atom) directly form a bond. When r is 0, a direct bond is formed between MN. ]

[In general formula [5],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluoro At least one selected from (phosphonyl) imide anion,
F is a fluorine atom,
M is any one selected from the group consisting of group 13 elements (Al, B), group 14 elements (Si), and group 15 elements (P, As, Sb), O is an oxygen atom,
N is a nitrogen atom.
Y is a carbon atom or a sulfur atom, q is 1 when Y is a carbon atom, and q is 1 or 2 when Y is a sulfur atom.
X is a carbon atom or a sulfur atom. When X is a carbon atom, r is 1, and when X is a sulfur atom, r is 1 or 2.
R ⁶ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can also be used. ), or -N (R ⁷⁾ - represents a. At this time, R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can take a branched chain or a cyclic structure.
R ⁹ and R ¹⁰ are each independently a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom, and in the case of 3 or more carbon atoms, a branched chain Alternatively, a ring structure can be used. Moreover, you may have a cyclic structure containing each other like following General formula [6].

c is 0 or 1; when n is 1, c is 0 (when c is 0, D does not exist); when n is 2, c is 1.
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, and s is 0 or 1. When p is 0, a direct bond is formed between Y and X.
When s is 0, N (R ⁹ ) (R ¹⁰ ) and R ⁶ are directly bonded, and at this time, structures such as the following [7] to [10] can also be taken. In the case of [8] and [10] in which the direct bond is a double bond, R ¹⁰ does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [9]. In this case, R ¹¹ and R ¹² are each independently a hydrogen atom or a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom, and having 3 or more carbon atoms. In that case, a branched chain or cyclic structure can be used. )

By subsequent studies by the inventors, non-aqueous electrolyte battery non-aqueous electrolytes containing no silane compound represented by the above general formula [2] or ionic complexes represented by the above general formulas [3] to [5] Even in the case of a water electrolyte, it has been found that the effect of suppressing an increase in internal resistance at a low temperature and the effect of suppressing the amount of gas generated at a high temperature can be exerted in a balanced manner as compared with a conventional electrolyte. Invented.

［１］

［一般式［１］中、Ｒ¹〜Ｒ³ は、それぞれ互いに独立して、フッ素原子、炭素数が１〜１０の直鎖あるいは分岐状のアルキル基、炭素数が１〜１０の直鎖あるいは分岐状のアルコキシ基、炭素数が２〜１０のアルケニル基、炭素数が２〜１０のアルケニルオキシ基、炭素数が２〜１０のアルキニル基、炭素数が２〜１０のアルキニルオキシ基、炭素数が３〜１０のシクロアルキル基、炭素数が３〜１０のシクロアルコキシ基、炭素数が３〜１０のシクロアルケニル基、炭素数が３〜１０のシクロアルケニルオキシ基、炭素数が６〜１０のアリール基、及び、炭素数が６〜１０のアリールオキシ基から選ばれる有機基であり、その有機基中にフッ素原子、酸素原子、不飽和結合が存在することもできる。但し、Ｒ¹〜Ｒ³の少なくとも１つはフッ素原子である。Ｍ^m+は、アルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンであり、ｍは該当するカチオンの価数と同数の整数を表す。］

Ｓｉ（Ｒ⁴）_a（Ｒ⁵）_4-a ［２］

［一般式［２］において、
Ｒ⁴は、それぞれ互いに独立して炭素−炭素不飽和結合を有する基を表す。Ｒ⁵は、それぞれ互いに独立して炭素数が１〜１０の直鎖あるいは分岐状のアルキル基を示し、これらの基は、フッ素原子及び／又は酸素原子を有していても良い。aは、２〜４の整数である。］

［一般式［３］において、
Ａ^b+は、金属イオン、プロトン及びオニウムイオンからなる群から選ばれる少なくとも１つであり、
Ｆは、フッ素原子であり、
Ｍは、１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれる少なくとも１つであり、
Ｏは、酸素原子であり、
Ｓは、硫黄原子である。
Ｒ⁶は、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ⁷）−を表す。このとき、Ｒ⁷は、水素原子、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ⁷は、分岐鎖あるいは環状構造をとることもできる。
Ｙは、炭素原子又は硫黄原子である。Ｙが炭素原子である場合、ｒは、１である。Ｙが硫黄原子である場合、ｒは、１又は２である。
ｂは、１又は２、ｏは、２又は４、ｎは、１又は２、ｐは、０又は１、ｑは、１又は２、ｒは、０、１又は２である。ｐが０の場合、Ｓ−Ｙ間に直接結合を形成する。］

［一般式［４］において、
Ａ^b+は、金属イオン、プロトン及びオニウムイオンからなる群から選ばれる少なくとも１つであり、
Ｆは、フッ素原子であり、
Ｍは、１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれる少なくとも１つであり、
Ｏは、酸素原子であり、
Ｎは、窒素原子である。
Ｙは、炭素原子又は硫黄原子であり、Ｙが炭素原子である場合、ｑは、１であり、Ｙが硫黄原子である場合、ｑは、１又は２である。
Ｒ⁶は、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ⁷）−を表す。このとき、Ｒ⁷は、水素原子、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ⁷は、分岐鎖あるいは環状構造をとることもできる。
Ｒ⁸は、水素原子、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ⁷）−を表す。このとき、Ｒ⁷は、水素原子、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ⁷は、分岐鎖あるいは環状構造をとることもできる。
ｂは、１又は２、ｏは、２又は４、ｎは、１又は２、ｐは、０又は１、ｑは、１又は２、ｒは、０又は１である。ｐが０の場合、Ｒ⁶の両隣に位置する原子同士（すなわち、Ｙと炭素原子）が直接結合を形成する。ｒが０の場合Ｍ−Ｎ間に直接結合を形成する。］

［一般式［５］において、
Ｄは、ハロゲンイオン、ヘキサフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ビス（トリフルオロメタンスルホニル）イミドアニオン、ビス（フルオロスルホニル）イミドアニオン、（フルオロスルホニル）（トリフルオロメタンスルホニル）イミドアニオン、ビス（ジフルオロホスホニル）イミドアニオンから選ばれる少なくとも一つであり、
Ｆは、フッ素原子であり、
Ｍは、１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれるいずれか１つであり
Ｏは、酸素原子であり、
Ｎは、窒素原子である。
Ｙは、炭素原子又は硫黄原子であり、Ｙが炭素原子である場合、ｑは、１であり、Ｙが硫黄原子である場合、ｑは、１又は２である。
Ｘは、炭素原子又は硫黄原子であり、Ｘが炭素原子である場合、ｒは、１であり、Ｘが硫黄原子である場合、ｒは、１又は２である。
Ｒ⁶は、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ⁷）−を表す。このとき、Ｒ⁷は、水素原子、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ⁷は、分岐鎖あるいは環状構造をとることもできる。
Ｒ⁹及びＲ¹⁰は、それぞれ独立で炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。また、下記一般式［６］の様にお互いを含む環状構造を有しても良い。

ｃは、０又は１であり、ｎが１の場合、ｃは、０（ｃが０のときＤは存在しない）であり、ｎが２の場合、ｃは、１となる。
ｏは、２又は４、ｎは、１又は２、ｐは、０又は１、ｑは、１又は２、ｒは、１又は２、ｓは、０又は１である。ｐが０の場合、Ｙ−Ｘ間に直接結合を形成する。
ｓが０の場合、Ｎ（Ｒ⁹）（Ｒ¹⁰）とＲ⁶は、直接結合し、その際は下記の［７］〜［１０］のような構造をとることもできる。直接結合が二重結合となる［８］、［１０］の場合、Ｒ¹⁰は、存在しない。また［９］の様に二重結合が環の外に出た構造を取ることも出来る。この場合のＲ¹¹、Ｒ¹²は、それぞれ独立で水素原子、又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。）

That is, the present invention provides a nonaqueous electrolytic solution for a nonaqueous electrolyte battery containing a nonaqueous solvent and a solute, containing at least hexafluorophosphate and / or tetrafluoroborate as a solute, and containing at least one kind of solute. It contains a salt having an imide anion represented by the following general formula [1] (hereinafter sometimes simply referred to as “salt having an imide anion”), and contains a silane compound represented by the following general formula [2]. The electrolyte solution for non-aqueous electrolyte batteries that does not contain the ionic complexes represented by the following general formulas [3] to [5] (hereinafter sometimes simply referred to as “non-aqueous electrolyte solution” or “electrolyte solution”) Is provided).

[1]

[In General Formula [1], R ^{1 to} R ³ are each independently a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 1 to 10 carbon atoms, or Branched alkoxy group, alkenyl group having 2 to 10 carbon atoms, alkenyloxy group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkynyloxy group having 2 to 10 carbon atoms, carbon number Is a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. An organic group selected from an aryl group and an aryloxy group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, and an unsaturated bond may be present in the organic group. However, at least one of R ^{1 to} R ³ is a fluorine atom. M ^{m +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. ]

Si (R ⁴ ) _a (R ⁵ ) _4-a [2]

[In general formula [2]
R ⁴ represents a group having a carbon-carbon unsaturated bond independently of each other. R ⁵ represents each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and these groups may have a fluorine atom and / or an oxygen atom. a is an integer of 2-4. ]

[In general formula [3],
A ^{b +} is at least one selected from the group consisting of metal ions, protons and onium ions,
F is a fluorine atom,
M is at least one selected from the group consisting of a group 13 element (Al, B), a group 14 element (Si), and a group 15 element (P, As, Sb);
O is an oxygen atom,
S is a sulfur atom.
R ⁶ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can also be used. ), or -N (R ⁷⁾ - represents a. At this time, R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can take a branched chain or a cyclic structure.
Y is a carbon atom or a sulfur atom. When Y is a carbon atom, r is 1. When Y is a sulfur atom, r is 1 or 2.
b is 1 or 2, o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, and r is 0, 1 or 2. When p is 0, a direct bond is formed between S and Y. ]

[In the general formula [4]
A ^{b +} is at least one selected from the group consisting of metal ions, protons and onium ions,
F is a fluorine atom,
M is at least one selected from the group consisting of a group 13 element (Al, B), a group 14 element (Si), and a group 15 element (P, As, Sb);
O is an oxygen atom,
N is a nitrogen atom.
Y is a carbon atom or a sulfur atom, q is 1 when Y is a carbon atom, and q is 1 or 2 when Y is a sulfur atom.
R ⁶ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can also be used. ), or -N (R ⁷⁾ - represents a. At this time, R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can take a branched chain or a cyclic structure.
R ⁸ represents a hydrogen atom, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, it has a branched chain or cyclic structure). Or -N (R ⁷ )-. At this time, R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can take a branched chain or a cyclic structure.
b is 1 or 2, o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, and r is 0 or 1. When p is 0, atoms located on both sides of R ⁶ (that is, Y and a carbon atom) directly form a bond. When r is 0, a direct bond is formed between MN. ]

[In general formula [5],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluoro At least one selected from (phosphonyl) imide anion,
F is a fluorine atom,
M is any one selected from the group consisting of group 13 elements (Al, B), group 14 elements (Si), and group 15 elements (P, As, Sb), O is an oxygen atom,
N is a nitrogen atom.
Y is a carbon atom or a sulfur atom, q is 1 when Y is a carbon atom, and q is 1 or 2 when Y is a sulfur atom.
X is a carbon atom or a sulfur atom. When X is a carbon atom, r is 1, and when X is a sulfur atom, r is 1 or 2.
R ⁶ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can also be used. ), or -N (R ⁷⁾ - represents a. At this time, R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can take a branched chain or a cyclic structure.
R ⁹ and R ¹⁰ are each independently a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. Alternatively, a ring structure can be used. Moreover, you may have a cyclic structure containing each other like following General formula [6].

When c is 0 or 1, when n is 1, c is 0 (D is not present when c is 0), and when n is 2, c is 1.
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, and s is 0 or 1. When p is 0, a direct bond is formed between Y and X.
When s is 0, N (R ⁹ ) (R ¹⁰ ) and R ⁶ are directly bonded, and in this case, the following structures [7] to [10] can be taken. In the case of [8] and [10] in which the direct bond is a double bond, R ¹⁰ does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [9]. In this case, R ¹¹ and R ¹² are each independently a hydrogen atom or a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom, and having 3 or more carbon atoms. In that case, a branched chain or cyclic structure can be used. )

“Not contained” in the electrolytic solution means that the concentration of the total amount of the compounds represented by the general formula [2] and the general formulas [3] to [5] in the total amount of the electrolytic solution is less than 5 mass ppm. means. The concentration of the silane compound represented by the general formula [2] in the electrolytic solution can be measured, for example, by gas chromatography. Moreover, the density | concentration of the ionic complex shown by the said general formula [3]-[5] in electrolyte solution can be measured by IR (infrared spectroscopy), for example.

Although the mechanism for improving battery characteristics according to the present invention is not clear, the salt having an imide anion represented by the general formula [1] is present at the interface between the positive electrode and the electrolytic solution and at the interface between the negative electrode and the electrolytic solution. It is thought that partly decomposes to form a film. This film suppresses direct contact between the non-aqueous solvent or solute and the active material to prevent decomposition of the non-aqueous solvent or solute, and suppresses deterioration of battery performance (increased resistance or generation of gas). Although the mechanism is not clear, it is important that the imide anion has both a phosphoryl moiety (—P (═O) R) and a sulfone moiety (—S (═O) ₂ R). Incorporation of both the phosphoryl moiety and the sulfone moiety is considered to be a stronger and more lithium conductive film, that is, a film with low resistance (film with good output characteristics). . Furthermore, the above effect is that the imide anion contains a portion having a high electron-withdrawing property (for example, a fluorine atom or a fluorine-containing alkoxy group). It is considered that a good film is formed. Further, when a hexafluorophosphate anion or a tetrafluoroborate anion is contained, a composite film containing these fluorides is formed, and it is estimated that a more stable film is formed even at a high temperature. For the above reasons, it is presumed that the non-aqueous electrolyte of the present invention exhibits a good balance between the effect of improving the low-temperature output characteristics and the effect of suppressing the amount of gas generated during high-temperature storage.

When the salt having the imide anion has at least one PF bond or SF bond, excellent low temperature characteristics can be obtained. As the number of PF bonds and SF bonds in the salt having the imide anion is larger, the low temperature characteristics can be further improved. In the salt having the imide anion represented by the general formula [1], It is more preferable that R ^{1 to} R ³ are all fluorine atoms.

In the salt having an imide anion represented by the general formula [1],
At least one of R ^{1 to} R ³ is a fluorine atom;
It is preferable that at least one of R ^{1 to} R ³ is a compound selected from a hydrocarbon group having 6 or less carbon atoms which may contain a fluorine atom.

In the salt having an imide anion represented by the general formula [1],
At least one of R ^{1 to} R ³ is a fluorine atom;
At least one of R ^{1 to} R ³ is a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxyl group, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a 2-propynyl group, or 2-propynyloxy. Group, phenyl group, phenyloxy group, 2,2-difluoroethyl group, 2,2-difluoroethyloxy group, 2,2,2-trifluoroethyl group, 2,2,2-trifluoroethyloxy group, 2 , 2,3,3-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyloxy group, 1,1,1,3,3,3-hexafluoroisopropyl group, and 1,1,1, A compound selected from 3,3,3-hexafluoroisopropyloxy groups is preferred.

The counter cation of the salt having an imide anion represented by the general formula [1] is preferably selected from the group consisting of lithium ions, sodium ions, potassium ions, and tetraalkylammonium ions.

Further, as the solute, LiPF ₂ (C ₂ O ₄ ) ₂ , LiPF ₄ (C ₂ O ₄ ), LiP (C ₂ O ₄ ) ₃ , LiBF ₂ (C ₂ O ₄ ), LiB (C ₂ O ₄ ) ₂ , LiPO ₂ F ₂ , LiN (F ₂ PO) ₂ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (FSO ₂ ), LiSO ₃ F, NaPF ₂ ( C ₂ O ₄ ) ₂ , NaPF ₄ (C ₂ O ₄ ), NaP (C ₂ O ₄ ) ₃ , NaBF ₂ (C ₂ O ₄ ), NaB (C ₂ O ₄ ) ₂ , NaPO ₂ F ₂ , NaN ( At least one selected from the group consisting of F ₂ PO) ₂ , NaN (FSO ₂ ) ₂ , NaSO ₃ F, NaN (CF ₃ SO ₂ ) ₂ , and NaN (CF ₃ SO ₂ ) (FSO ₂ ). May be.

The amount of the salt having an imide anion represented by the general formula [1] is 0.005 with respect to the total amount of the salt having the imide anion represented by the nonaqueous solvent, the solute, and the general formula [1]. It is preferable to be in the range of ˜12.0 mass%. When the content exceeds 12.0% by mass, the viscosity of the electrolytic solution increases and the characteristics may deteriorate at low temperatures. When the content is less than 0.005% by mass, the formation of the film becomes insufficient. There is a fear that the effect of improving the characteristics is difficult to be exhibited.

The salt having an imide anion represented by the general formula [1] is preferably highly pure, and in particular, Cl (chlorine) is contained in the salt having the imide anion as a raw material before being dissolved in the electrolytic solution. The amount is preferably 5000 ppm by mass or less, and more preferably 1000 ppm by mass or less.

Moreover, the lower the free acid concentration in the electrolytic solution, the more preferable because the positive electrode active material and the current collector of the nonaqueous electrolytic battery are less likely to be corroded. The free acid concentration is preferably 600 ppm by mass or less, and more preferably 120 ppm by mass or less.

The electrolyte solution further includes vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, 1,6-diisocyanatohexane, ethynyl ethylene carbonate, trans-difluoroethylene carbonate, propane sultone, propene sultone, 1,3,2 -Dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, 1,2-ethanedisulfonic anhydride, tris (trimethylsilyl) borate, succino At least one additive selected from the group consisting of nitrile, (ethoxy) pentafluorocyclotriphosphazene, t-butylbenzene, t-amylbenzene, fluorobenzene, and cyclohexylbenzene. May be.

The non-aqueous solvent is at least one selected from the group consisting of cyclic carbonates, chain carbonates, cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. Is preferred. It is more preferable that cyclic carbonate is contained, and it is particularly preferable to contain one or more selected from ethylene carbonate, propylene carbonate, fluoroethylene carbonate, vinylene carbonate, and vinyl ethylene carbonate.

Moreover, this invention is a nonaqueous electrolyte battery provided with the positive electrode, the negative electrode, and said electrolyte solution for nonaqueous electrolyte batteries at least.

When used in a non-aqueous electrolyte battery, the electrolytic solution of the present invention can exhibit a good balance between the effect of suppressing an increase in internal resistance at low temperatures and the effect of suppressing the amount of gas generated at high temperatures.

Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is an example of an embodiment of the present invention, and the specific contents thereof are not limited. Various modifications can be made within the scope of the gist.

1. Non-aqueous electrolyte battery electrolyte The non-aqueous electrolyte battery electrolyte of the present invention is a non-aqueous electrolyte battery non-aqueous electrolyte containing a non-aqueous solvent and a solute, and at least hexafluorophosphate as a solute. And / or containing a tetrafluoroborate, containing at least one salt having an imide anion represented by the above general formula [1], and not containing a silane compound represented by the above general formula [2], An electrolyte solution for a non-aqueous electrolyte battery that does not contain the ionic complex represented by the above general formulas [3] to [5].

1-1. Regarding the salt having an imide anion represented by the general formula [1], in the general formula [1], it is important that at least one of R ^{1 to} R ³ is a fluorine atom. The reason is not clear, but unless at least one is a fluorine atom, the effect of suppressing the internal resistance of a battery using the electrolytic solution is not sufficient.

In the above general formula [1], the alkyl group and alkoxyl group represented by R ^{1 to} R ³ are methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, third Butyl, pentyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, and 1,1,1,3,3,3 -The C1-C10 alkyl group and fluorine-containing alkyl groups, such as a hexafluoro isopropyl group, and the alkoxy group induced | guided | derived from these groups are mentioned.
Examples of the alkenyl group and alkenyloxy group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, and 1,3-butadienyl group, and fluorine-containing groups. Examples include alkenyl groups and alkenyloxy groups derived from these groups.
Alkynyl group and alkynyloxy group are derived from alkynyl group having 2 to 10 carbon atoms such as ethynyl group, 2-propynyl group and 1,1dimethyl-2-propynyl group, fluorine-containing alkynyl group, and these groups. An alkynyloxy group.
Examples of the cycloalkyl group and the cycloalkoxy group include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group, a fluorinated cycloalkyl group, and a cycloalkoxy group derived from these groups.
The cycloalkenyl group and the cycloalkenyloxy group include a cycloalkenyl group having 3 to 10 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group, a fluorine-containing cycloalkenyl group, and a cycloalkenyloxy group derived from these groups. Is mentioned.
Examples of the aryl group and aryloxy group include aryl groups having 6 to 10 carbon atoms such as phenyl group, tolyl group, and xylyl group, fluorine-containing aryl groups, and aryloxy groups derived from these groups.

As an anion of the salt having an imide anion represented by the general formula [1], more specifically, for example, the following compound No. 1-No. 18 etc. are mentioned. However, the salt having an imide anion used in the present invention is not limited by the following examples.

As the salt having an imide anion represented by the general formula [1], at least one of R ^{1 to} R ³ is a fluorine atom, and at least one of R ^{1 to} R ³ may contain a fluorine atom. A compound selected from 6 or less hydrocarbon groups is preferred. If the hydrocarbon group has more than 6 carbon atoms, the internal resistance when a film is formed on the electrode tends to be relatively large. When the number of carbon atoms is 6 or less, the above-mentioned internal resistance tends to be smaller, which is preferable. Fluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 1,1,1,3,3,3-hexafluoro When at least one group selected from an isopropyl group, and an alkoxy group, an alkenyloxy group, or an alkynyloxy group derived from these groups, a non-aqueous electrolyte battery capable of exhibiting a good balance between cycle characteristics and internal resistance characteristics is obtained. Therefore, it is preferable.

The salt having an imide anion represented by the general formula [1] is preferably highly pure, and in particular, Cl (chlorine) is contained in the salt having the imide anion as a raw material before being dissolved in the electrolytic solution. The amount is preferably 5000 ppm by mass or less, more preferably 1000 ppm by mass or less, and still more preferably 100 ppm by mass or less. Use of a salt having an imide anion in which Cl (chlorine) remains at a high concentration is not preferable because the battery member tends to be corroded.

The salt having an imide anion represented by the general formula [1] can be produced by various methods. Although it does not limit as a manufacturing method, For example, it can obtain with the following method.
A method in which a corresponding phosphoric acid amide (H ₂ NP (═O) R ¹ R ² ) and a corresponding sulfonyl halide (R ³ SO ₂ X; X is a halogen atom) are reacted in the presence of an organic base or an inorganic base.
A method in which a corresponding sulfonylamide (H ₂ NSO ₂ R ³ ) and a corresponding phosphoryl halide (R ¹ R ² P (═O) X; X is a halogen atom) are reacted in the presence of an organic base or an inorganic base.
Further, as shown in patent documents (CN101654229A, CN102617414A), after obtaining a salt having an imide anion in which the fluorine atom portion of the salt having a corresponding imide anion is a halogen atom other than a fluorine atom, Can be obtained.

The addition amount of the salt having an imide anion used in the present invention is preferably a lower limit relative to the total amount of the salt having an imide anion represented by the non-aqueous solvent described later, the solute described later, and the general formula [1]. 0.005 mass% or more, preferably 0.05 mass% or more, more preferably 0.1 mass% or more, and a suitable upper limit is 12.0 mass% or less, preferably 6.0 mass% or less, More preferably, it is 3.0 mass% or less.
If the amount added is less than 0.005% by mass, the effect of improving battery characteristics is hardly obtained, which is not preferable. On the other hand, if the addition amount exceeds 12.0% by mass, not only is it not possible to obtain further effects, but it is not preferable because resistance is increased due to excessive film formation and deterioration of battery performance is likely to occur. . These salts having an imide anion may be used alone as long as they do not exceed 12.0% by mass, and two or more kinds may be used in any combination and ratio according to the application. Also good.

1-2. Solute The electrolyte solution for a non-aqueous electrolyte battery of the present invention contains at least hexafluorophosphate and / or tetrafluoroborate as a solute.
In addition, the type of other solute that may coexist with the hexafluorophosphate and / or tetrafluoroborate used in the electrolyte for a nonaqueous electrolyte battery of the present invention is not particularly limited, and any electrolyte salt Can be used. As a specific example, in the case of a lithium battery and a lithium ion battery, LiPF ₂ (C ₂ O ₄ ) ₂ , LiPF ₄ (C ₂ O ₄ ), LiP (C ₂ O ₄ ) ₃ , LiBF ₂ (C ₂ O _{4), LiB (C 2 O} 4) 2, LiPO 2 F 2, LiN (F 2 PO) 2, LiN (FSO 2) 2, LiN (CF 3 SO 2) 2, LiClO 4, LiAsF 6, LiSbF 6, LiCF ₃ SO ₃ , LiSO ₃ F, LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (FSO ₂ ), LiC (CF ₃ SO ₂ ) ₃ , LiPF ₃ (C ₃ F ₇ ) ₃ , LiB (CF ₃ ) ₄ , LiBF ₃ (C ₂ F ₅ ) and the like. In the case of a sodium ion battery, NaPF ₂ (C ₂ O ₄ ) ₂ , NaPF ₄ (C _{2 O 4), NaP (C 2} O 4) 3, NaBF 2 (C 2 O 4), Na _{(C 2 O 4) 2,} NaPO 2 F 2, NaN (F 2 PO) 2, NaN (FSO 2) 2, NaN (CF 3 SO 2) 2, NaClO 4, NaAsF 6, NaSbF 6, NaCF 3 SO 3 , NaSO ₃ F, NaN (C ₂ F ₅ SO ₂ ) ₂ , NaN (CF ₃ SO ₂ ) (FSO ₂ ), NaC (CF ₃ SO ₂ ) ₃ , NaPF ₃ (C ₃ F ₇ ) ₃ , NaB (CF ₃ ) ₄ and electrolyte salts represented by NaBF ₃ (C ₂ F ₅ ) and the like. One kind of these solutes may be used alone, or two or more kinds of solutes may be mixed and used in any combination and ratio according to the application. Among these, considering the energy density, output characteristics, life, etc. of the battery, LiPF ₂ (C ₂ O ₄ ) ₂ , LiPF ₄ (C ₂ O ₄ ), LiP (C ₂ O ₄ ) ₃ , LiBF ₂ (C ₂ O ₄ ), LiB (C ₂ O ₄ ) ₂ , LiPO ₂ F ₂ , LiN (F ₂ PO) ₂ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ( FSO ₂ ), LiSO ₃ F, NaPF ₂ (C ₂ O ₄ ) ₂ , NaPF ₄ (C ₂ O ₄ ), NaP (C ₂ O ₄ ) ₃ , NaBF ₂ (C ₂ O ₄ ), NaB (C ₂ O ₄ ) ₂ , NaPO ₂ F ₂ , NaN (F ₂ PO) ₂ , NaN (FSO ₂ ) ₂ , NaN (CF ₃ SO ₂ ) ₂ , NaSO ₃ F, and NaN (CF ₃ SO ₂ ) (FSO ₂ ) Is preferred.

Suitable combinations of the above solutes include, for example, LiPF ₂ (C ₂ O ₄ ) ₂ , LiPF ₄ (C ₂ O ₄ ), LiP (C ₂ O ₄ ) ₃ , LiBF ₂ (C ₂ O ₄ ), LiB ( C ₂ O ₄ ) ₂ , LiPO ₂ F ₂ , LiN (F ₂ PO) ₂ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) _2, LiN (CF ₃ SO ₂ ) (FSO ₂ ), LiSO ₃ A combination of at least one selected from the group consisting of F and LiPF ₆ is preferred.

As solutes, LiPF ₂ (C ₂ O ₄ ) ₂ , LiPF ₄ (C ₂ O ₄ ), LiP (C ₂ O ₄ ) ₃ , LiBF ₂ (C ₂ O ₄ ), LiB (C ₂ O ₄ ) ₂ , LiPO ₂ F ₂ , LiN (F ₂ PO) ₂ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (FSO ₂ ), at least selected from the group consisting of LiSO ₃ F one ratio when used in combination with LiPF ₆ (molar ratio when the LiPF ₆ was 1 mol) is usually 1: 0.001: 0.5, preferably 1: 0.01 It is in the range of ˜1: 0.2. Using a combination of solutes at the above ratios has the effect of further improving various battery characteristics. On the other hand, if the ratio of LiPF ₆ is lower than 1: 0.5, the ionic conductivity of the electrolytic solution tends to decrease and the resistance tends to increase.

The concentration of these solutes (the concentration combined with hexafluorophosphate and / or tetrafluoroborate) is not particularly limited, but the preferred lower limit is 0.5 mol / L or more, preferably 0.7 mol / L. More preferably, it is 0.9 mol / L or more, and a suitable upper limit is 2.5 mol / L or less, preferably 2.0 mol / L or less, more preferably 1.5 mol / L or less. If the concentration is less than 0.5 mol / L, the ionic conductivity tends to decrease and the cycle characteristics and output characteristics of the nonaqueous electrolyte battery tend to decrease. On the other hand, if the concentration exceeds 2.5 mol / L, the nonaqueous electrolyte battery is used. When the viscosity of the electrolytic solution increases, the ionic conductivity also tends to be lowered, and the cycle characteristics and output characteristics of the nonaqueous electrolytic battery may be lowered.

When a large amount of the solute is dissolved in the non-aqueous solvent at once, the temperature of the non-aqueous electrolyte may increase due to the heat of dissolution of the solute. When the liquid temperature rises remarkably, decomposition of the lithium salt containing fluorine atoms is accelerated and hydrogen fluoride may be generated. Hydrogen fluoride is not preferable because it causes deterioration of battery performance. For this reason, although the liquid temperature at the time of melt | dissolving this solute in a nonaqueous solvent is not specifically limited, -20-80 degreeC is preferable and 0-60 degreeC is more preferable.

1-3. About nonaqueous solvent The kind of nonaqueous solvent used for the electrolyte solution for nonaqueous electrolyte batteries of this invention is not specifically limited, Arbitrary nonaqueous solvents can be used. Specific examples include propylene carbonate (hereinafter sometimes referred to as “PC”), ethylene carbonate (hereinafter sometimes referred to as “EC”), cyclic carbonates such as butylene carbonate, diethyl carbonate (hereinafter referred to as “ DEC ”), chain carbonates such as dimethyl carbonate (hereinafter sometimes referred to as“ DMC ”), ethyl methyl carbonate (hereinafter sometimes referred to as“ EMC ”), γ- Cyclic esters such as butyrolactone, γ-valerolactone, chain esters such as methyl acetate, methyl propionate, ethyl propionate (hereinafter sometimes referred to as “EP”), tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, etc. Cyclic ether, dimethoxyethane, diethyl ether, etc. Examples include sulfone compounds such as chain ether, dimethyl sulfoxide, sulfolane, and sulfoxide compounds. Moreover, although a category differs from a nonaqueous solvent, an ionic liquid etc. can also be mentioned. Moreover, the nonaqueous solvent used for this invention may be used individually by 1 type, and may mix and use two or more types by arbitrary combinations and a ratio according to a use. Among these, from the viewpoint of the electrochemical stability with respect to the oxidation-reduction and the chemical stability related to the reaction with heat and the above solute, in particular, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propion. Methyl acid and ethyl propionate are preferred.
For example, when the nonaqueous solvent contains at least one kind from a cyclic carbonate having a high dielectric constant and at least one kind from a chain carbonate or a chain ester having a low liquid viscosity, the ionic conductivity of the electrolytic solution is preferably increased. Specifically, those including the following combinations are more preferable.
(1) Combination of EC and EMC,
(2) Combination of EC and DEC,
(3) Combination of EC, DMC and EMC,
(4) Combination of EC, DEC and EMC,
(5) Combination of EC, EMC and EP,
(6) Combination of PC and DEC,
(7) Combination of PC and EMC,
(8) Combination of PC and EP,
(9) Combination of PC, DMC and EMC,
(10) Combination of PC, DEC and EMC,
(11) Combination of PC, DEC and EP,
(12) Combination of PC, EC and EMC,
(13) Combination of PC, EC, DMC and EMC,
(14) Combination of PC, EC, DEC and EMC,
(15) Combination of PC, EC, EMC and EP

1-4. The above is an explanation of the basic structure of the electrolyte for a non-aqueous electrolyte battery of the present invention, but as long as the gist of the present invention is not impaired, the electrolyte for a non-aqueous electrolyte battery of the present invention is used. You may add the additive generally used in arbitrary ratios. Specific examples include cyclohexylbenzene, biphenyl, t-butylbenzene, t-amylbenzene, fluorobenzene, vinylene carbonate (hereinafter sometimes referred to as “VC”), vinylethylene carbonate, difluoroanisole, fluoroethylene carbonate (hereinafter referred to as “VC”). May be described as "FEC"), 1,6-diisocyanatohexane, ethynylethylene carbonate, trans-difluoroethylene carbonate, propane sultone, propene sultone, dimethyl vinylene carbonate, 1,3,2-dioxathiolane-2 , 2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, 1,2-ethanedisulfonic anhydride, tris (trimethylsilyl) borane DOO, succinonitrile, include compounds having the (ethoxy) pentafluoro cyclotriphosphazene such overcharging prevention effect, negative electrode film-forming effect and the positive protective effect. Further, alkali metal salts other than the solutes (lithium salts, sodium salts) and salts (lithium salts, sodium salts) having the imide anion represented by the general formula [1] (however, the general formulas [3] to [5] May be used as an additive. Specific examples include carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate, and sulfate esters such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, and sodium methyl sulfate. .
Moreover, it is also possible to use the non-aqueous electrolyte battery electrolyte in a quasi-solid state with a gelling agent or a crosslinked polymer as used in a non-aqueous electrolyte battery called a lithium polymer battery.

Moreover, the electrolyte solution for non-aqueous electrolyte batteries of the present invention includes a plurality of types of the solute (lithium salt, sodium salt) or a salt having an imide anion represented by the general formula [1] according to required characteristics. (Lithium salt, sodium salt) may be used in combination, and the total of alkali metal salts may be four or more.
For example, when four kinds of lithium salts are contained, one kind is used from the solutes of lithium hexafluorophosphate and lithium tetrafluoroborate (hereinafter sometimes referred to as “first solute”), and LiPF ₄ (C ₂ O ₄ ), LiPF ₂ (C ₂ O ₄ ) ₂ , LiP (C ₂ O ₄ ) ₃ , LiBF ₂ (C ₂ O ₄ ), LiB (C ₂ O ₄ ) ₂ , LiPO ₂ F ₂ , LiN (F _{2 PO) 2, LiN (FSO 2} ) 2, LiN (CF 3 SO 2) 2, LiClO 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiSO 3 F, LiN (C 2 F 5 SO 2) 2, LiN Solutes such as (CF ₃ SO ₂ ) (FSO ₂ ), LiC (CF ₃ SO ₂ ) ₃ , LiPF ₃ (C ₃ F ₇ ) ₃ , LiB (CF ₃ ) ₄ , LiBF ₃ (C ₂ F ₅ ) 1 type from “may be described as“ second solute ”), general formula The compound as a salt having an imide anion represented by 1] No. 2 types of lithium salts such as 1-18 are used,
It is conceivable to use one from the first solute, two from the second solute, and one from the lithium salt having the imide anion.
In particular,
(1) LiPF ₆ and Compound No. No. 5 lithium salt and compound no. A combination of 6 lithium salts and LiPF ₂ (C ₂ O ₄ ) ₂ ;
(2) LiPF ₆ and Compound No. No. 1 lithium salt and compound no. A combination of 15 lithium salts and LiPO ₂ F ₂ ;
(3) LiPF ₆ and Compound No. 1 lithium salt, a combination of LiPO ₂ F ₂ and LiN (F ₂ PO) ₂ ,
(4) LiPF ₆ and Compound No. A combination of lithium salt 5 and LiPF ₂ (C ₂ O ₄ ) ₂ and LiPO ₂ F ₂ ;
When four lithium salts are contained as described above, the effect of suppressing an increase in internal resistance at low temperatures is greater, which is preferable.
Moreover, you may add together the said other additives other than those as needed.
Furthermore, the total of the alkali metal salts may be five or more. For example, when five types of lithium salts are contained, one compound is used from the first solute, one compound is used from the second solute, and the compound No. 1 is used. 3 types of lithium salts such as 1-18 are used,
One compound from the first solute and two compounds from the second solute are used. 2 types of lithium salts such as 1-18 are used,
One compound from the first solute and three compounds from the second solute are used. One type of lithium salt such as 1-18 may be used.
In particular,
(1) LiPF ₆ and Compound No. No. 5 lithium salt and compound no. A combination of lithium salt 6 and LiPF ₄ (C ₂ O ₄ ) and LiPF ₂ (C ₂ O ₄ ) ₂ ;
(2) LiPF ₆ and Compound No. 1 lithium salt, LiBF ₂ (C ₂ O ₄ ), LiPO ₂ F ₂ and LiSO ₃ F in combination,
(3) LiPF ₆ and Compound No. No. 1 lithium salt and compound no. A combination of lithium salt 6 and LiN (F ₂ PO) ₂ and LiPO ₂ F ₂ ;
(4) LiPF ₆ and Compound No. A combination of lithium salt 5 and LiPF ₄ (C ₂ O ₄ ), LiPF ₂ (C ₂ O ₄ ) ₂ and LiPO ₂ F ₂ ;
(5) LiPF ₆ and Compound No. 5 lithium salt, LiBF ₂ (C ₂ O ₄ ), LiPO ₂ F ₂ and LiSO ₃ F in combination,
When five lithium salts are contained as described above, the effect of suppressing gas generation at high temperatures is greater, which is preferable. If necessary, other lithium salts (the above additives) may be added in combination.

2. Next, the configuration of the nonaqueous electrolyte battery of the present invention will be described. The non-aqueous electrolyte battery according to the present invention is characterized by using the above-described electrolyte for a non-aqueous electrolyte battery according to the present invention, and the other components are those used in general non-aqueous electrolyte batteries. Is used. That is, it comprises a positive electrode and a negative electrode capable of inserting and extracting lithium, a current collector, a separator, a container, and the like.

The negative electrode material is not particularly limited, but in the case of lithium batteries and lithium ion batteries, lithium metal, alloys of lithium metal and other metals, or intermetallic compounds and various carbon materials (artificial graphite, natural graphite, etc.), Metal oxides, metal nitrides, tin (simple substance), tin compounds, silicon (simple substance), silicon compounds, activated carbon, conductive polymers, and the like are used.
Examples of the carbon material include graphitizable carbon, non-graphitizable carbon (hard carbon) having a (002) plane spacing of 0.37 nm or more, and graphite having a (002) plane spacing of 0.34 nm or less. Etc. More specifically, there are thermally decomposable carbon, cokes, glassy carbon fiber, organic polymer compound fired body, activated carbon or carbon black. Among these, coke includes pitch coke, needle coke, petroleum coke, and the like. The organic polymer compound fired body is obtained by firing and carbonizing a phenol resin, a furan resin, or the like at an appropriate temperature. A carbon material is preferable because a change in crystal structure associated with insertion and extraction of lithium is very small, so that a high energy density and excellent cycle characteristics can be obtained. The shape of the carbon material may be any of fibrous, spherical, granular or scale-like. In addition, amorphous carbon or a graphite material coated with amorphous carbon on the surface is more preferable because the reactivity between the material surface and the electrolytic solution becomes low.

The positive electrode material is not particularly limited, but in the case of lithium batteries and lithium ion batteries, for example, lithium-containing transition metal composite oxides such as LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , and lithium-containing transition metals A composite oxide in which a plurality of transition metals such as Co, Mn, Ni, etc. are mixed, a part of the transition metal in the lithium-containing transition metal composite oxide is replaced with a metal other than the transition metal, olivine and LiFePO _4, LiCoPO _4, phosphoric acid compound of a transition metal such as LiMnPO ₄ called, oxides such as _{TiO 2, V 2 O 5,} MoO 3, TiS 2, sulfides such as FeS, or polyacetylene, polyparaphenylene, polyaniline , And conductive polymers such as polypyrrole, activated carbon, polymers that generate radicals, carbon materials, etc. It is use.

Acetylene black, ketjen black, carbon fiber, graphite as a conductive material, polytetrafluoroethylene, polyvinylidene fluoride, SBR resin, polyimide, etc. as a binder are added to the positive electrode and negative electrode materials, and then molded into a sheet shape. Thus, an electrode sheet can be obtained.

  As a separator for preventing contact between the positive electrode and the negative electrode, a nonwoven fabric or a porous sheet made of polypropylene, polyethylene, paper, glass fiber, or the like is used.

  A non-aqueous electrolyte battery having a coin shape, a cylindrical shape, a square shape, an aluminum laminate sheet shape or the like is assembled from each of the above elements.

A non-aqueous electrolyte battery includes (a) the non-aqueous electrolyte described above, (b) a positive electrode, (c) a negative electrode, and (d) a separator as described below. It may be a battery.
The non-aqueous electrolyte battery is [(b) positive electrode]
(A) The positive electrode preferably contains at least one oxide and / or polyanion compound as a positive electrode active material.
[Positive electrode active material]
In the case of a lithium ion secondary battery in which the cation in the non-aqueous electrolyte is mainly lithium, (a) the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials that can be charged and discharged. For example, (A) a lithium transition metal composite oxide containing at least one metal selected from nickel, manganese and cobalt and having a layered structure, (B) a lithium manganese composite oxide having a spinel structure, (C) What contains at least 1 sort (s) from the lithium containing olivine type | mold phosphate and the lithium excess layered transition metal oxide which has (D) layered rock salt type structure is mentioned.
((A) lithium transition metal composite oxide)
Cathode active material (A) Examples of lithium transition metal composite oxides containing at least one metal selected from nickel, manganese and cobalt and having a layered structure include lithium-cobalt composite oxides and lithium-nickel composite oxides. Lithium / nickel / cobalt composite oxide, lithium / nickel / cobalt / aluminum composite oxide, lithium / cobalt / manganese composite oxide, lithium / nickel / manganese composite oxide, lithium / nickel / manganese / cobalt composite oxide Etc. In addition, some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, Sn. Those substituted with other elements such as may also be used.
Specific examples of the lithium-cobalt composite oxide and the lithium-nickel composite oxide include LiCoO ₂ , LiNiO ₂ and lithium cobaltate to which a different element such as Mg, Zr, Al, Ti is added (LiCo _0.98 Mg _0.01 Zr _0.01 O ₂ , LiCo _0.98 Mg _0.01 Al _0.01 O ₂ , LiCo _0.975 Mg _0.01 Zr _0.005 Al _0.01 O _2, etc.), lithium cobaltate with a rare earth compound fixed to the surface described in WO2014 / 034043, etc. may be used. . Further, as described in Japanese Patent Application Laid-Open No. 2002-151077 and the like, a part of the particle surface of LiCoO ₂ particle powder coated with aluminum oxide may be used.
The lithium / nickel / cobalt composite oxide and the lithium / nickel / cobalt / aluminum composite oxide are represented by formula (1-1).
Li _a Ni _1-bc Co _b M ¹ _c O ₂ (1-1)
In formula (1-1), M ¹ is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, and B, a is 0.9 ≦ a ≦ 1.2, b , C satisfy the conditions of 0.1 ≦ b ≦ 0.3 and 0 ≦ c ≦ 0.1.
These can be prepared, for example, according to the production method described in JP2009-137835A. _{Specifically, LiNi 0.8 Co 0.2 O 2,} LiNi 0.85 Co 0.10 Al 0.05 O 2, LiNi 0.87 Co 0.10 Al 0.03 O 2, LiNi 0.6 Co 0.3 Al 0.1 O 2 and the like.
Specific examples of the lithium / cobalt / manganese composite oxide and the lithium / nickel / manganese composite oxide include LiNi _0.5 Mn _0.5 O ₂ and LiCo _0.5 Mn _0.5 O ₂ .
Examples of the lithium / nickel / manganese / cobalt composite oxide include a lithium-containing composite oxide represented by the general formula (1-2).
_{Li d Ni e Mn f Co g} M 2 h O 2 (1-2)
In Formula (1-2), M ² is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, B, and Sn, and d is 0.9 ≦ d ≦ 1.2. , E, f, g, and h satisfy the conditions of e + f + g + h = 1, 0 ≦ e ≦ 0.7, 0 ≦ f ≦ 0.5, 0 ≦ g ≦ 0.5, and h ≧ 0.
The lithium / nickel / manganese / cobalt composite oxide contains manganese in the range represented by the general formula (1-2) in order to enhance the structural stability and improve the safety at a high temperature in the lithium secondary battery. In particular, in order to improve the high rate characteristics of the lithium ion secondary battery, it is more preferable to further contain cobalt in the range represented by the general formula (1-2).
Specifically, for example, Li [Ni _1/3 Mn _1/3 Co _1/3 ] O ₂ , Li [Ni _0.45 Mn _0.35 Co _0.2 ] O ₂ , Li [ Ni _0.5 Mn _0.3 Co _0.2 ] O ₂ , Li [Ni _0.6 Mn _0.2 Co _0.2 ] O ₂ , Li [Ni _0.49 Mn _0.3 Co _0.2 Zr _0.01 ] O ₂ , Li [Ni _0.49 Mn _0.3 Co _0.2 Mg _0.01 ] O _2, etc. Is mentioned.
((B) lithium manganese composite oxide having spinel structure)
As a lithium manganese complex oxide which has a positive electrode active material (B) spinel structure, the spinel type lithium manganese complex oxide shown by General formula (1-3) is mentioned, for example.
Li _j (Mn _2−k M ³ _k ) O ₄ (1-3)
In Formula (1-3), M ³ is at least one metal element selected from the group consisting of Ni, Co, Fe, Mg, Cr, Cu, Al, and Ti, and j is 1.05 ≦ j ≦ 1.15 and k is 0 ≦ k ≦ 0.20.
Specifically, for example, LiMn ₂ O ₄ , LiMn _1.95 Al _0.05 O ₄ , LiMn _1.9 Al _0.1 O ₄ , LiMn _1.9 Ni _0.1 O ₄ , LiMn _1.5 Ni _0.5 O _{4 and the} like can be mentioned.
((C) Lithium-containing olivine-type phosphate)
As a positive electrode active material (C) lithium containing olivine type | mold phosphate, what is shown by General formula (1-4) is mentioned, for example.
LiFe _1-n M ⁴ _n PO ₄ (1-4)
In formula (1-4), M ⁴ is at least one selected from Co, Ni, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr, and Cd, and n is 0 ≦ n ≦ 1.
Specifically, for example, LiFePO ₄ , LiCoPO ₄ , LiNiPO ₄ , LiMnPO _{4 and the} like can be mentioned, among which LiFePO ₄ and / or LiMnPO ₄ are preferable.
((D) lithium-excess layered transition metal oxide)
Examples of the lithium-excess layered transition metal oxide having a positive electrode active material (D) layered rock salt structure include those represented by general formula (1-5).
xLiM ⁵ O _2. (1-x) Li ₂ M ⁶ O ₃ (1-5)
In formula (1-5), x is a number satisfying 0 <x <1, M ⁵ is at least one metal element having an average oxidation number of 3 ⁺ , and M ⁶ is an average oxidation It is at least one metal element whose number is 4 ⁺ . In formula (1-5), M ⁵ is preferably one metal element selected from trivalent Mn, Ni, Co, Fe, V, and Cr. The average oxidation number of these metals may be trivalent.
In formula (1-5), M ⁶ is preferably one or more metal elements selected from Mn, Zr, and Ti. Specifically, 0.5 [LiNi _0.5 Mn _0.5 O ₂ ] · 0.5 [Li ₂ MnO ₃ ], 0.5 [LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ] · 0.5 [Li ₂ MnO ₃ ], 0.5 [LiNi _0.375 Co _0.25 Mn _0.375 O ₂ ] · 0.5 [Li ₂ MnO ₃ ], 0.5 [LiNi _0.375 Co _0.125 Fe _0.125 Mn _0.375 O ₂ ] · 0.5 [Li ₂ MnO ₃ ], 0.45 [LiNi _0.375 Co _0.25 Mn _0.375 O ₂ ] · 0.10 [Li ₂ TiO ₃ ] · 0.45 [Li ₂ MnO ₃ ] and the like.
It is known that the positive electrode active material (D) represented by the general formula (1-5) expresses a high capacity at a high voltage charge of 4.4 V (Li standard) or more (for example, US Pat. , 135,252 specification).
These positive electrode active materials can be prepared according to, for example, the production methods described in JP 2008-270201 A, WO 2013/118661, JP 2013-030284 A, and the like.
The positive electrode active material may contain at least one selected from the above (A) to (D) as a main component, but other examples include FeS ₂ , TiS ₂ , V ₂ O. ₅ , transition element chalcogenides such as MoO ₃ and MoS ₂ , conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, polymers that generate radicals, and carbon materials.
[Positive electrode current collector]
(A) The positive electrode has a positive electrode current collector. As the positive electrode current collector, for example, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used.
[Positive electrode active material layer]
(A) In the positive electrode, for example, a positive electrode active material layer is formed on at least one surface of the positive electrode current collector. A positive electrode active material layer is comprised by the above-mentioned positive electrode active material, a binder, and a electrically conductive agent as needed, for example.
Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, or styrene butadiene rubber (SBR) resin.
As the conductive agent, for example, a carbon material such as acetylene black, ketjen black, carbon fiber, or graphite (granular graphite or flake graphite) can be used. In the positive electrode, it is preferable to use acetylene black or ketjen black having low crystallinity.
[(C) Negative electrode]
(C) The negative electrode preferably contains at least one negative electrode active material.
[Negative electrode active material]
In the case of a lithium ion secondary battery in which the cation in the non-aqueous electrolyte is mainly lithium, (c) as the negative electrode active material constituting the negative electrode, lithium ion can be doped / dedoped. For example, (E) a carbon material in which the d value of the lattice plane (002 plane) in X-ray diffraction is 0.340 nm or less, and (F) carbon whose d value of the lattice plane (002 plane) in X-ray diffraction exceeds 0.340 nm A material, (G) an oxide of one or more metals selected from Si, Sn, Al, (H) one or more metals selected from Si, Sn, Al, alloys containing these metals, or these metals or alloys; Examples include an alloy with lithium and (I) at least one selected from lithium titanium oxide. These negative electrode active materials can be used individually by 1 type, and can also be used in combination of 2 or more type.
((E) Carbon material whose d-value on the lattice plane (002 plane) in X-ray diffraction is 0.340 nm or less)
Examples of the carbon material having a d value of the lattice plane (002 plane) in the negative electrode active material (E) X-ray diffraction of 0.340 nm or less include pyrolytic carbons, cokes (for example, pitch coke, needle coke, petroleum coke). Etc.), graphites, organic polymer compound fired bodies (for example, those obtained by firing and carbonizing a phenol resin, furan resin, etc.), carbon fibers, activated carbon, etc., which are graphitized Good. The carbon material has a (002) plane spacing (d002) of 0.340 nm or less measured by an X-ray diffraction method, among which graphite having a true density of 1.70 g / cm ³ or more, or A highly crystalline carbon material having close properties is preferred.
((F) Carbon material whose d value of the lattice plane (002 plane) in X-ray diffraction exceeds 0.340 nm)
As the carbon material in which the d value of the lattice plane (002 plane) in the negative electrode active material (F) X-ray diffraction exceeds 0.340 nm, amorphous carbon can be mentioned. Is a carbon material whose stacking order hardly changes. Examples thereof include non-graphitizable carbon (hard carbon), mesocarbon microbeads (MCMB) baked at 1500 ° C. or less, and mesopause bitch carbon fibers (MCF). A typical example is Carbotron (registered trademark) P manufactured by Kureha Co., Ltd.
((G) One or more metal oxides selected from Si, Sn, and Al)
Negative electrode active material (G) One or more metal oxides selected from Si, Sn, and Al can be doped / dedoped with lithium ions, such as silicon oxide and tin oxide. It is done.
Examples include SiO _x having a structure in which ultrafine particles of Si are dispersed in SiO ₂ . When this material is used as the negative electrode active material, since Si that reacts with Li is ultrafine particles, the charge and discharge are performed smoothly, while the SiO _x particles having the above structure itself have a small surface area, so that the negative electrode active material layer The coating properties and the adhesion of the negative electrode mixture layer to the current collector when the composition (paste) is used to form the film are also good.
Since SiO _x has a large volume change due to charge / discharge, high capacity and good charge / discharge cycle characteristics can be obtained by using SiO _x and graphite of the negative electrode active material (E) in a specific ratio in combination with the negative electrode active material. And both.
((H) one or more metals selected from Si, Sn, Al, alloys containing these metals, or alloys of these metals or alloys and lithium)
Negative electrode active material (H) One or more metals selected from Si, Sn, Al, alloys containing these metals, or alloys of these metals or alloys and lithium include, for example, metals such as silicon, tin, and aluminum, silicon An alloy, a tin alloy, an aluminum alloy, etc. are mentioned, The material which these metals and alloys alloyed with lithium with charging / discharging can also be used.
Specific examples of these are, for example, simple metals such as silicon (Si) and tin (Sn) described in WO 2004/100343 and JP-A-2008-016424 (for example, in powder form). , The metal alloy, a compound containing the metal, an alloy containing tin (Sn) and cobalt (Co) in the metal, and the like. When the metal is used for an electrode, a high charge capacity can be expressed, and the volume expansion / contraction associated with charge / discharge is relatively small, which is preferable. Moreover, when these metals are used for the negative electrode of a lithium ion secondary battery, they are known to exhibit a high charge capacity because they are alloyed with Li during charging, which is also preferable in this respect.
Further, for example, a negative electrode active material formed of silicon micro pillars with a submicron diameter, a negative electrode active material composed of fibers made of silicon, and the like described in publications such as WO 2004/042851 and WO 2007/083155 are used. May be.
((I) lithium titanium oxide)
Examples of the negative electrode active material (I) lithium titanium oxide include lithium titanate having a spinel structure and lithium titanate having a ramsdellite structure.
Examples of lithium titanate having a spinel structure include Li _{4 + α} Ti ₅ O ₁₂ (α varies within a range of 0 ≦ α ≦ 3 due to a charge / discharge reaction). Examples of lithium titanate having a ramsdellite structure include Li _{2 + β} Ti ₃ O ₇ (β varies within a range of 0 ≦ β ≦ 3 due to charge / discharge reaction). These negative electrode active materials can be prepared according to the production methods described in, for example, JP-A No. 2007-018883 and JP-A No. 2009-176752.
For example, in the case of a sodium ion secondary battery in which the cation in the non-aqueous electrolyte is mainly sodium, hard carbon, oxides such as TiO ₂ , V ₂ O ₅ , and MoO ₃ are used as the negative electrode active material. For example, in the case of a sodium ion secondary battery in which the cation in the non-aqueous electrolyte is mainly sodium, a sodium-containing transition metal composite oxide such as NaFeO ₂ , NaCrO ₂ , NaNiO ₂ , NaMnO ₂ , NaCoO ₂ as the positive electrode active material, Those containing transition metals such as Fe, Cr, Ni, Mn, Co, etc., of these sodium-containing transition metal composite oxides, some of the transition metals of these sodium-containing transition metal composite oxides other than other transition metals Substituted by metals, transition metal phosphate compounds such as Na ₂ FeP ₂ O ₇ , NaCo ₃ (PO ₄ ) ₂ P ₂ O ₇ , sulfides such as TiS ₂ and FeS ₂ , polyacetylene, polypara Conductive polymers such as phenylene, polyaniline, and polypyrrole, activated carbon, polymers that generate radicals, and carbon materials are used.
[Negative electrode current collector]
(C) The negative electrode has a negative electrode current collector. As the negative electrode current collector, for example, copper, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used.
[Negative electrode active material layer]
(C) In the negative electrode, for example, a negative electrode active material layer is formed on at least one surface of the negative electrode current collector. A negative electrode active material layer is comprised by the above-mentioned negative electrode active material, a binder, and a electrically conductive agent as needed, for example.
Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, or styrene butadiene rubber (SBR) resin.
As the conductive agent, for example, a carbon material such as acetylene black, ketjen black, carbon fiber, or graphite (granular graphite or flake graphite) can be used.
[Production method of electrode ((b) positive electrode and (c) negative electrode)]
The electrode is obtained, for example, by dispersing and kneading an active material, a binder, and, if necessary, a conductive agent in a solvent such as N-methyl-2-pyrrolidone (NMP) or water at a predetermined blending amount. The paste can be applied to a current collector and dried to form an active material layer. The obtained electrode is preferably compressed by a method such as a roll press to adjust the electrode to an appropriate density.
[(D) Separator]
The non-aqueous electrolyte battery includes (d) a separator. (A) As a separator for preventing the contact between the positive electrode and the (c) negative electrode, a nonwoven fabric or a porous sheet made of polyolefin such as polypropylene or polyethylene, cellulose, paper, glass fiber or the like is used. These films are preferably microporous so that the electrolyte can penetrate and ions can easily pass therethrough.
Examples of the polyolefin separator include a membrane that electrically insulates the positive electrode and the negative electrode and allows lithium ions to pass therethrough, such as a microporous polymer film such as a porous polyolefin film. As a specific example of the porous polyolefin film, for example, a porous polyethylene film alone or a porous polyethylene film and a porous polypropylene film may be overlapped and used as a multilayer film. Moreover, the composite film etc. of the porous polyethylene film and the polypropylene film are mentioned.
[Exterior body]
In configuring the nonaqueous electrolyte battery, as the exterior body of the nonaqueous electrolyte battery, for example, a metal can such as a coin type, a cylindrical shape, and a square shape, or a laminate exterior body can be used. Examples of the metal can material include nickel-plated steel plates, stainless steel plates, nickel-plated stainless steel plates, aluminum or alloys thereof, nickel, and titanium.
As the laminate outer package, for example, an aluminum laminate film, a SUS laminate film, a laminate film made of silica-coated polypropylene, polyethylene, or the like can be used.
The configuration of the non-aqueous electrolyte battery according to the present embodiment is not particularly limited. For example, an electrode element in which a positive electrode and a negative electrode are arranged to face each other and a non-aqueous electrolyte are included in an exterior body. It can be set as a structure. The shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device having a shape such as a coin shape, a cylindrical shape, a square shape, or an aluminum laminate sheet type is assembled from the above elements.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by this Example.

[Example 1-1]
Table 1 shows the preparation conditions of the non-aqueous electrolyte, and Table 2 shows the evaluation results of the battery using the electrolyte. In addition, each value of -30 degreeC internal resistance characteristic and gas generation amount of the battery of Table 2 is electrolyte solution No .. It is a relative value when the internal resistance after the charging / discharging cycle test of the laminate cell produced using A-35 and the gas generation amount accompanying the cycle test are set to 100, respectively.

A mixed solvent of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate in a volume ratio of 3: 3: 4 was used as the non-aqueous solvent, and the imide was added so that LiPF ₆ had a concentration of 1.0 mol / L as a solute in the solvent. As a salt having an anion, Compound No. 1 lithium salt (the Cl content in the salt having the imide anion as a raw material before being dissolved in the electrolyte is 50 ppm by mass) is 1 to the total amount of the salt having a nonaqueous solvent, a solute, and an imide anion. The non-aqueous electrolyte battery electrolyte No. 1 was dissolved to a concentration of 0% by mass. A-1 was prepared. Said preparation was performed maintaining the liquid temperature in the range of 20-30 degreeC. In addition, the density | concentration of the total amount of the compound shown by General formula [2]-[5] in electrolyte solution was less than 5 mass ppm, and the free acid density | concentration was 45 mass ppm.

Using the above electrolytic solution, a cell was produced using LiNi _1/3 Co _1/3 Mn _1/3 O ₂ as a positive electrode material and graphite as a negative electrode material, and the cycle characteristics and internal resistance characteristics of the battery were actually evaluated. The test cell was produced as follows.

Mixing 90% by mass of LiNi _1/3 Co _1/3 Mn _1/3 O ₂ powder with 5% by mass of 5% by mass of polyvinylidene fluoride (hereinafter referred to as “PVDF”) as a binder and 5% by mass of acetylene black as a conductive material, Further, N-methylpyrrolidone was added to make a paste. The paste was applied on an aluminum foil and dried to obtain a test positive electrode body.
Further, 90% by mass of graphite powder was mixed with 10% by mass of PVDF as a binder, and N-methylpyrrolidone was further added to form a slurry. This slurry was applied on a copper foil and dried at 120 ° C. for 12 hours to obtain a test negative electrode body.
Then, an electrolytic solution was immersed in a polyethylene separator to assemble a 50 mAh cell with an aluminum laminate exterior.

[Evaluation of internal resistance characteristics (-30 ° C)]
A charge / discharge test at an environmental temperature of 70 ° C. was performed using the above cell. Both charging and discharging were performed at a current density of 3.5 mA / cm ^2. After charging reached 4.3 V, 4.3 V was maintained for 1 hour, and discharging was performed up to 3.0 V, and the charge / discharge cycle was repeated. The cell after 300 cycles was charged to 4.3 V at an ambient temperature of 25 ° C. and a current density of 0.35 mA / cm ² , and then the internal resistance of the battery was measured at an ambient temperature of −30 ° C.

[Gas generation evaluation]
Before and after the cycle test at 70 ° C., the amount of gas generation was evaluated by estimating the amount of increase in the cell volume by the buoyancy method using silicon oil.

^*電解液No.A-44、A-45 は質量％

^* Electrolyte Nos. A-44 and A-45 are mass%

[Examples 1-2 to 1-34]
The nonaqueous electrolyte solution No. 1 was prepared in the same procedure as in Example 1-1 except that the preparation conditions for the nonaqueous electrolyte solution shown in Table 1 were followed. A-2 to A-34 were prepared and evaluated in the same manner. Table 2 shows the evaluation results of the battery using the electrolytic solution. In addition, Cl content in the salt which has the imide anion used in the Example was 200 mass ppm or less altogether. Moreover, all the free acid concentrations in the electrolyte solution used in the examples were 100 mass ppm or less. In addition, each value of -30 degreeC internal resistance characteristic and gas generation amount of the battery of Table 2 is electrolyte solution No .. It is a relative value when the internal resistance after the cycle of the laminated cell produced using A-35 and the gas generation amount accompanying the cycle test are set to 100, respectively.

[Comparative Examples 1-1 to 1-3, Reference Examples 1-1 and 1-2]
The nonaqueous electrolyte solution No. 1 was prepared in the same procedure as in Example 1-1 except that the preparation conditions for the nonaqueous electrolyte solution shown in Table 1 were followed. A-35 to A-37, A-44, and A-45 were prepared and evaluated in the same manner. In addition, Comparative Examples 1-1 to 1-3 are experimental examples relating to an electrolytic solution that does not contain a salt having an imide anion or does not contain a solute, respectively. Reference Example 1-1 is an experimental example relating to an electrolytic solution containing a compound represented by the general formula [2], and Reference Example 1-2 is an experimental example relating to an electrolytic solution containing a compound represented by the general formula [5]. Table 2 shows the evaluation results of the battery using the electrolytic solution. In addition, each value of -30 degreeC internal resistance characteristic and gas generation amount of the battery of Table 2 is electrolyte solution No .. It is a relative value when the internal resistance after the cycle of the laminated cell produced using A-35 and the gas generation amount accompanying the cycle test are set to 100, respectively.

（＊比較例１−１の値を１００とした場合の相対値）

(* Relative value when the value of Comparative Example 1-1 is 100)

[Comparative Examples 1-4, 1-5]
The nonaqueous electrolyte solution No. 1 was prepared in the same procedure as in Example 1-1 except that the preparation conditions for the nonaqueous electrolyte solution shown in Table 1 were followed. A-38 and A-39 were prepared and evaluated similarly. In addition, Comparative Example 1-4 and 1-5 are respectively the following compound No. as a salt which has an imide anion. 19, no. It is an experiment example regarding the electrolyte solution using 20 lithium salts. In addition, Cl content in the salt which has the imide anion used by Comparative Examples 1-4 and 1-5 was 90 mass ppm and 20 mass ppm, respectively. Moreover, the free acid concentration in the electrolyte solution used in Comparative Examples 1-4 and 1-5 was 42 mass ppm and 40 mass ppm, respectively. Table 3 shows the evaluation results of the battery using the electrolytic solution. In addition, each value of -30 degreeC internal resistance characteristic and gas generation amount of the battery of Table 3 is electrolyte solution No .. It is a relative value when the internal resistance after the cycle of the laminated cell produced using A-35 (Comparative Example 1-1) and the gas generation amount accompanying the cycle test are 100 respectively.

Compound No. 19 Compound No. 20

（＊比較例１−１の値を１００とした場合の相対値）

(* Relative value when the value of Comparative Example 1-1 is 100)

[Comparative Example 1-6]
The nonaqueous electrolyte solution No. 1 was prepared in the same procedure as in Example 1-1 except that the preparation conditions for the nonaqueous electrolyte solution shown in Table 1 were followed. A-40 was prepared and evaluated similarly. In addition, Comparative Example 1-6 is the following compound No. 1 as a salt having an imide anion. It is an experiment example regarding the electrolyte solution using the lithium salt of 21. In addition, Cl content in the salt which has the imide anion used by Comparative Example 1-6 was 5 mass ppm. Moreover, the free acid concentration in the electrolyte solution used in Comparative Example 1-6 was 37 mass ppm. Table 4 shows the evaluation results of the battery using the electrolytic solution. The values of −30 ° C. internal resistance characteristics and gas generation amount of the batteries in Table 4 are the electrolyte No. It is a relative value when the internal resistance after the cycle of the laminated cell produced using A-35 (Comparative Example 1-1) and the gas generation amount accompanying the cycle test are 100 respectively.

Compound No. 21

（＊比較例１−１の値を１００とした場合の相対値）

(* Relative value when the value of Comparative Example 1-1 is 100)

[Comparative Example 1-7]
The nonaqueous electrolyte solution No. 1 was prepared in the same procedure as in Example 1-1 except that the preparation conditions for the nonaqueous electrolyte solution shown in Table 1 were followed. A-41 was prepared and evaluated similarly. In addition, Comparative Example 1-7 is the following compound No. 1 as a salt having an imide anion. It is an experiment example regarding the electrolyte solution using 22 lithium salts. In addition, Cl content in the salt which has the imide anion used by Comparative Example 1-7 was 60 mass ppm. Moreover, the free acid concentration in the electrolytic solution used in Comparative Example 1-7 was 46 mass ppm. Table 5 shows the evaluation results of the battery using the electrolytic solution. The values of −30 ° C. internal resistance characteristics and gas generation amount of the batteries in Table 5 are the electrolyte solution No. It is a relative value when the internal resistance after the cycle of the laminated cell produced using A-35 (Comparative Example 1-1) and the gas generation amount accompanying the cycle test are 100 respectively.

Compound No. 22

（＊比較例１−１の値を１００とした場合の相対値）

(* Relative value when the value of Comparative Example 1-1 is 100)

[Comparative Example 1-8]
The nonaqueous electrolyte solution No. 1 was prepared in the same procedure as in Example 1-1 except that the preparation conditions for the nonaqueous electrolyte solution shown in Table 1 were followed. A-42 was prepared and evaluated similarly. In addition, Comparative Example 1-8 is the following compound No. 1 as a salt having an imide anion. It is an experiment example regarding the electrolyte solution using 23 lithium salt. In addition, Cl content in the salt which has the imide anion used in Comparative Example 1-8 was 110 mass ppm. Moreover, the free acid concentration in the electrolytic solution used in Comparative Example 1-8 was 36 mass ppm. Table 6 shows the evaluation results of the battery using the electrolytic solution. In addition, each value of -30 degreeC internal resistance characteristic and gas generation amount of the battery of Table 6 is electrolyte solution No. It is a relative value when the internal resistance after the cycle of the laminated cell produced using A-35 (Comparative Example 1-1) and the gas generation amount accompanying the cycle test are 100 respectively.

Compound No. 23

（＊比較例１−１の値を１００とした場合の相対値）

(* Relative value when the value of Comparative Example 1-1 is 100)

[Comparative Example 1-9]
The nonaqueous electrolyte solution No. 1 was prepared in the same procedure as in Example 1-1 except that the preparation conditions for the nonaqueous electrolyte solution shown in Table 1 were followed. A-43 was prepared and evaluated similarly. In addition, Comparative Example 1-9 is the following compound No. 1 as a salt having an imide anion. It is an experiment example regarding the electrolyte solution using 24 lithium salts. In addition, Cl content in the salt which has the imide anion used by Comparative Example 1-9 was 20 mass ppm. Moreover, the free acid concentration in the electrolytic solution used in Comparative Example 1-9 was 39 mass ppm. Table 7 shows the evaluation results of the battery using the electrolytic solution. The values of −30 ° C. internal resistance characteristics and gas generation amounts of the batteries in Table 7 are the electrolyte solution No. It is a relative value when the internal resistance after the cycle of the laminated cell produced using A-35 (Comparative Example 1-1) and the gas generation amount accompanying the cycle test are 100 respectively.

（＊比較例１−１の値を１００とした場合の相対値）

(* Relative value when the value of Comparative Example 1-1 is 100)

  When the results in Table 2 are compared, the internal resistance characteristics are good when hexafluorophosphate and / or tetrafluoroborate is contained and a salt having an imide anion represented by the above general formula [1] is contained. Further, the gas generation amount after the cycle is suppressed. When the salt having the imide anion of the present invention is not included (Comparative Examples 1-1 and 1-2), only the salt having the imide anion of the present invention is not included, and no hexafluorophosphate and / or tetrafluoroborate is included. In the case (Comparative Example 1-3), the internal resistance is relatively high and the amount of gas generated is also relatively large. On the other hand, when both the salt having the imide anion of the present invention and the hexafluorophosphate and / or tetrafluoroborate were contained, good internal resistance characteristics and a gas generation amount suppressing effect were exhibited.

  Further, from the results of Tables 3 to 7, when comparing salts having an imide anion having the same substituent, a salt having an imide anion containing only a phosphorus atom or only a sulfur atom was used (Comparative Example 1- 4-1-7, 1-9), when a salt having an imide anion that does not contain both a PF bond and an SF bond (Comparative Examples 1-6, 1-8, 1-9), The internal resistance is relatively high and the amount of gas generated is also relatively large. On the other hand, when the salt having an imide anion of the present invention was contained, good internal resistance characteristics and a gas generation amount suppressing effect were shown.

[Examples 2-1 to 2-47, Comparative Examples 2-1 to 2-30] <Experimental example 1 when other solutes and additives are added>
A non-aqueous electrolyte No. 1 was prepared in the same procedure as in Example 1-1 except that the non-aqueous electrolyte preparation conditions shown in Table 8 were followed. B-1 to B-77 were prepared and evaluated in the same manner. Each electrolytic solution contains 1.0 mol / L of LiPF ₆ as a solute, and the concentration of the total amount of the compounds represented by the general formulas [2] to [5] in the electrolytic solution is less than 5 ppm by mass. Moreover, all the free acid concentrations in the electrolyte solution used in the examples were 120 mass ppm or less.
Table 9 shows the evaluation results of the battery using the electrolytic solution. In addition, the respective values of the −30 ° C. internal resistance characteristics and the gas generation amount of the batteries in Table 9 are the internal resistance after the cycle of the laminate cell produced using the electrolyte solution containing no salt having the imide anion of the present invention. , And relative values when the amount of gas generated in the cycle test is 100, respectively.

* In Examples 2-1 to 2-6 and Comparative Examples 2-1 and 2-2, relative values when the value of Comparative Example 2-1 was set to 100 Examples 2-7 and 2-8, Comparative Example 2 -3, relative values when the value of Comparative Example 2-3 is 100, and Examples 2-9 to 2-10, and Comparative Example 2-4 is relative when the value of Comparative Example 2-4 is 100 In Examples 2-11 to 2-12 and Comparative Example 2-5, relative values in Examples 2-13 to 2-14 and Comparative Example 2-6 when the value of Comparative Example 2-5 was set to 100, Relative value when the value of Comparative Example 2-6 is set to 100 In Examples 2-15 to 2-16 and Comparative Examples 2-7 and 2-8, the relative value when the value of Comparative Example 2-8 is set to 100 In Examples 2-17 to 2-18 and Comparative Example 2-9, relative values in Examples 2-19 to 2-20 and Comparative Example 2-10 when the value of Comparative Example 2-9 was set to 100, Comparative Example 2- Relative values when the value of 0 is set to 100 Relative values of Examples 2-21 to 2-22 and Comparative Example 2-11 When the value of Comparative Example 2-11 is set to 100, Examples 2-23 to 2 −24, in Comparative Example 2-12, the relative value when the value of Comparative Example 2-12 was set to 100 Example 2-25 to 2-26, and in Comparative Example 2-13, the value of Comparative Example 2-13 was Relative values in Examples 2-27 to 2-28 and Comparative Example 2-14 with 100, relative values in Examples 2-29 to 2-30 with Comparative Example 2-14 as 100, and comparison In Examples 2-15 and 2-16, relative values when the value of Comparative Example 2-16 is set to 100, Examples 2-31 to 2-32, and Comparative Example 2-17, the values of Comparative Example 2-17 are set. Relative value when set to 100 In Examples 2-33 to 2-34 and Comparative Example 2-18, the value of Comparative Example 2-18 was set to 100 In the relative values of Examples 2-35 to 2-36 and Comparative Example 2-19, the relative values of Example 2-37 and Comparative Example 2-20 in which the value of Comparative Example 2-19 is 100 are shown in Comparative Example 2. Relative value in Example 2-38 and Comparative Example 2-21 when the value of −20 is set to 100 In Comparative Example 2-21, the relative value of Example 2-39 and Comparative Example 2 in which the value of Comparative Example 2-21 is set to 100 22 is a relative value example 2-40 when the value of Comparative Example 2-22 is 100, and Comparative Example 2-23 is a relative value example 2 when the value of Comparative Example 2-23 is 100. 41, in Comparative Example 2-24, relative value when the value of Comparative Example 2-24 is 100, Example 2-42, and in Comparative Example 2-25, the value of Comparative Example 2-25 is 100 In the relative value example 2-43 and the comparative example 2-26, the relative value example 2- when the value of the comparative example 2-26 is set to 100 is used. 44, in Comparative Example 2-27, the relative value when the value of Comparative Example 2-27 is 100, Example 2-45, and in Comparative Example 2-28, the value of Comparative Example 2-28 is 100 In the relative value example 2-46 and the comparative example 2-29, the value of the comparative example 2-29 when the value of the comparative example 2-29 is 100. In the comparative example 2-30 and the comparative example 2-30, the value of the comparative example 2-30 Relative value when the value is 100

As described above, in any of the examples in which other solutes and additives are added to the electrolyte solution in addition to LiPF ₆ , the inside of the laminate cell using the electrolyte solution for a non-aqueous electrolyte battery of the present invention It was confirmed that the resistance characteristics and gas generation amount were superior to the corresponding comparative examples. Therefore, by using the non-aqueous electrolyte battery electrolyte of the present invention, a non-aqueous electrolyte battery exhibiting excellent internal resistance characteristics and gas generation amount suppression effect is obtained regardless of the type of other solutes and additives. It was shown that

[Examples 3-1 to 3-4, Comparative examples 3-1 to 3-4] <Experimental examples when the negative electrode body is changed>
A battery having a configuration in which the negative electrode body and the electrolyte used in Example 1-1 were changed as shown in Table 10 was evaluated in the same manner as in Example 1-1. The negative electrode body in which the negative electrode active material is Li ₄ Ti ₅ O ₁₂ is a mixture of 90% by mass of Li ₄ Ti ₅ O ₁₂ powder, 5% by mass of PVDF as a binder, and 5% by mass of acetylene black as a conductive agent, Further, N-methylpyrrolidone was added, and the obtained paste was coated on a copper foil and dried to produce a charge end voltage of 2.7 V and a discharge end voltage of 1.5 V at the time of battery evaluation. did. In Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-4, the values of the internal resistance characteristics and gas generation amount of the battery do not include the salt having the imide anion of the present invention. It is a relative value when the internal resistance after the cycle of the laminated cell produced using the electrolytic solution and the gas generation amount accompanying the cycle test are set to 100, respectively.

[Examples 4-1 to 4-5, Comparative Examples 4-1 to 4-5] <Experimental example when the negative electrode body is changed>
A battery having a configuration in which the negative electrode body and the electrolyte used in Example 1-1 were changed as shown in Table 10 was evaluated in the same manner as in Example 1-1. The negative electrode body in which the negative electrode active material is graphite (silicon-containing) is obtained by mixing 80% by mass of graphite powder with 10% by mass of silicon powder and 10% by mass of PVDF as a binder, and further adding N-methylpyrrolidone, The obtained paste was applied onto a copper foil and dried to prepare a charge end voltage and a discharge end voltage in the same manner as in Example 1-1. In Examples 4-1 to 4-5 and Comparative Examples 4-1 to 4-5, the values of the internal resistance characteristics and gas generation amount of the battery do not include the salt having the imide anion of the present invention. It is a relative value when the internal resistance after the cycle of the laminated cell produced using the electrolytic solution and the gas generation amount accompanying the cycle test are 100 respectively.

[Examples 5-1 to 5-4, Comparative Examples 5-1 to 5-4] <Experimental example when the negative electrode body is changed>
A battery having a configuration in which the negative electrode body and the electrolyte used in Example 1-1 were changed as shown in Table 10 was evaluated in the same manner as in Example 1-1. In addition, the negative electrode body in which the negative electrode active material is hard carbon is mixed with 90% by mass of hard carbon, 5% by mass of PVDF as a binder, and 5% by mass of acetylene black as a conductive agent, and further, N-methylpyrrolidone is added, The obtained paste was applied on a copper foil and dried to produce a charge end voltage of 4.2V and a discharge end voltage of 2.2V during battery evaluation. In Examples 5-1 to 5-4 and Comparative Examples 5-1 to 5-4, the values of the internal resistance characteristics and gas generation amount of the battery do not include the salt having the imide anion of the present invention. Relative values when the internal resistance after the cycle of the laminated cell produced using the electrolyte and the amount of gas generated by the cycle test are set to 100, respectively.

* In Examples 3-1 and 3-2 and Comparative Examples 3-1 and 3-2, relative values when the value of Comparative Example 3-1 is set to 100. Examples 3-3 and 3-4, Comparative Example 3 -3, 3-4, relative values when the value of Comparative Example 3-3 is 100, Examples 4-1 to 4-3, and Comparative Examples 4-1 to 4-3 are those of Comparative Example 4-1. Relative values when the value is 100 In Examples 4-4 and 4-5 and Comparative Examples 4-4 and 4-5, the relative value when the value of Comparative Example 4-4 is 100 Example 5-1 In 5-2 and Comparative Examples 5-1 and 5-2, relative values when the value of Comparative Example 5-1 is set to 100, Examples 5-3 and 5-4, Comparative Examples 5-3 and 5-4 Then, relative value when the value of Comparative Example 5-3 is 100

[Examples 6-1 to 6-4, Comparative Examples 6-1 to 6-4] <Experimental example when the positive electrode body is changed>
A battery having a configuration in which the positive electrode body and the electrolyte used in Example 1-1 were changed as shown in Table 11 was evaluated in the same manner as in Example 1-1. In addition, the positive electrode body in which the positive electrode active material is LiCoO ₂ is obtained by mixing 90% by mass of LiCoO ₂ powder with 5% by mass of PVDF as a binder and 5% by mass of acetylene black as a conductive material, and further adding N-methylpyrrolidone, The obtained paste was applied on an aluminum foil and dried. The end-of-charge voltage during battery evaluation was 4.2 V, and the end-of-discharge voltage was 3.0 V. In Examples 6-1 to 6-4 and Comparative Examples 6-1 to 6-4, each value of the internal resistance characteristics and gas generation amount of the battery does not include the salt having the imide anion of the present invention. It is a relative value when the internal resistance after the cycle of the laminated cell produced using the electrolytic solution and the gas generation amount accompanying the cycle test are set to 100, respectively.

[Examples 7-1 to 7-4, Comparative Examples 7-1 to 7-4] <Experimental example when the positive electrode body is changed>
A battery having a configuration in which the positive electrode body and the electrolyte used in Example 1-1 were changed as shown in Table 11 was evaluated in the same manner as in Example 1-1. The positive electrode body in which the positive electrode active material is LiNi _0.8 Co _0.15 Al _0.05 O ₂ is 5% by mass of 90% by mass of LiNi _0.8 Co _0.15 Al _0.05 O ₂ powder, 5% by mass of PVDF as a binder, and 5% by mass of acetylene black as a conductive material. The mixture was mixed, further N-methylpyrrolidone was added, and the resulting paste was applied on an aluminum foil and dried. The end-of-charge voltage during battery evaluation was 4.2 V, and the end-of-discharge voltage was 3.0 V. In Examples 7-1 to 7-4 and Comparative Examples 7-1 to 7-4, the values of the internal resistance characteristics and gas generation amount of the battery do not include the salt having the imide anion of the present invention. It is a relative value when the internal resistance after the cycle of the laminated cell produced using the electrolytic solution and the gas generation amount accompanying the cycle test are 100 respectively.

[Examples 8-1 to 8-4, Comparative Examples 8-1 to 8-4] <Experimental example when the positive electrode body is changed>
A battery having a configuration in which the positive electrode body and the electrolyte used in Example 1-1 were changed as shown in Table 11 was evaluated in the same manner as in Example 1-1. The positive electrode body in which the positive electrode active material is LiMn ₂ O ₄ is obtained by mixing 90% by mass of LiMn ₂ O ₄ powder with 5% by mass of PVDF as a binder and 5% by mass of acetylene black as a conductive material, and further N-methylpyrrolidone. The paste obtained was applied onto an aluminum foil and dried. The end-of-charge voltage during battery evaluation was 4.2 V, and the end-of-discharge voltage was 3.0 V. In Examples 8-1 to 8-4 and Comparative Examples 8-1 to 8-4, the values of the internal resistance characteristics and gas generation amount of the battery do not include the salt having the imide anion of the present invention. It is a relative value when the internal resistance after the cycle of the laminated cell produced using the electrolytic solution and the gas generation amount accompanying the cycle test are set to 100, respectively.

[Examples 9-1 to 9-4, Comparative Examples 9-1 to 9-4] <Experimental example when the positive electrode body is changed>
A battery having a configuration in which the positive electrode body and the electrolyte used in Example 1-1 were changed as shown in Table 11 was evaluated in the same manner as in Example 1-1. The positive electrode body in which the positive electrode active material is LiFePO ₄ is obtained by mixing 90% by mass of LiFePO ₄ powder coated with amorphous carbon with 5% by mass of PVDF as a binder and 5% by mass of acetylene black as a conductive material. N-methylpyrrolidone was added, and the resulting paste was applied on an aluminum foil and dried. The end-of-charge voltage during battery evaluation was 4.1 V, and the end-of-discharge voltage was 2.5 V. In Examples 9-1 to 9-4 and Comparative Examples 9-1 to 9-4, the values of the internal resistance characteristics and gas generation amount of the battery do not include the salt having the imide anion of the present invention. It is a relative value when the internal resistance after the cycle of the laminated cell produced using the electrolytic solution and the gas generation amount accompanying the cycle test are set to 100, respectively.

* In Examples 6-1 and 6-2 and Comparative Examples 6-1 and 6-2, relative values when the value of Comparative Example 6-1 is set to 100. Examples 6-3 and 6-4, Comparative Example 6 -3, 6-4, relative values when the value of Comparative Example 6-3 is 100, Examples 7-1 and 7-2, and Comparative Examples 7-1 and 7-2 are those of Comparative Example 7-1. Relative value when the value is 100 In Examples 7-3 and 7-4 and Comparative Examples 7-3 and 7-4, the relative value when the value of Comparative Example 7-3 is 100 Example 8-1 8-2 and Comparative Examples 8-1 and 8-2, relative values when the value of Comparative Example 8-1 is 100, Examples 8-3 and 8-4, Comparative Examples 8-3 and 8-4 Then, relative values when the value of Comparative Example 8-3 is set to 100 In Examples 9-1 and 9-2 and Comparative Examples 9-1 and 9-2, the value of Comparative Example 9-1 is set to 100 Relative values of Examples 9-3 and 9-4, Comparative Example 9-3 In 9-4, the relative value when the value of Comparative Example 9-3 as 100

As described above, in any example using Li ₄ Ti ₅ O ₁₂ , graphite (silicon-containing), and hard carbon as the negative electrode active material, the laminate using the non-aqueous electrolyte battery electrolyte of the present invention It was confirmed that the internal resistance characteristics and gas generation amount of the cell were superior to the corresponding comparative examples. Therefore, by using the non-aqueous electrolyte battery electrolyte of the present invention, it is possible to obtain a non-aqueous electrolyte battery exhibiting excellent internal resistance characteristics and a gas generation amount suppressing effect regardless of the type of the negative electrode active material. Indicated.

Further, as described above, in any example using LiCoO ₂ , LiNi _0.8 Co _0.15 Al _0.05 O ₂ , LiMn ₂ O ₄ , LiFePO ₄ as the positive electrode active material, the non-aqueous electrolyte battery of the present invention is used. It was confirmed that the internal resistance characteristics and gas generation amount of the laminate cell using the electrolytic solution were superior to the corresponding comparative examples. Therefore, by using the non-aqueous electrolyte battery electrolyte of the present invention, it is possible to obtain a non-aqueous electrolyte battery that exhibits excellent internal resistance characteristics and gas generation amount suppression effect regardless of the type of the positive electrode active material. Indicated.

[Example 10-1]
A mixed solvent of propylene carbonate, ethylene carbonate and diethyl carbonate in a volume ratio of 2: 2: 6 was used as the non-aqueous solvent, and the imide was added to the solvent so that NaPF ₆ had a concentration of 1.0 mol / L as a solute. As a salt having an anion, Compound No. 1 sodium salt (Cl content in the salt having the imide anion as a raw material before being dissolved in the electrolytic solution is 10 ppm by mass) is 1 with respect to the total amount of the salt having a nonaqueous solvent, a solute, and an imide anion. The resulting solution was dissolved to a concentration of 0.0% by mass, and an electrolyte for a non-aqueous electrolyte battery was prepared as shown in Table 12. The free acid concentration in the electrolyte was 12 mass ppm. The above preparation was performed while maintaining the liquid temperature at 25 ° C.

Using this electrolytic solution, a cell was prepared in the same manner as in Example 1-1 except that NaFe _0.5 Co _0.5 O ₂ was used as the positive electrode material and hard carbon was used as the negative electrode material, and the battery was evaluated in the same manner as in Example 1-1. Carried out. The positive electrode body in which the positive electrode active material is NaFe _0.5 Co _0.5 O ₂ is a mixture of 90% by mass of NaFe _0.5 Co _0.5 O ₂ powder and 5% by mass of PVDF as a binder and 5% by mass of acetylene black as a conductive material. N-methylpyrrolidone was added, and the obtained paste was applied on an aluminum foil and dried to prepare a final charge voltage of 3.8 V and a final discharge voltage of 1.5 V during battery evaluation. The evaluation results are shown in Table 13.

[Examples 10-2 to 10-18, Comparative Examples 10-1 to 10-9]
As shown in Table 12, a nonaqueous electrolyte battery electrolyte was prepared in the same manner as in Example 10-1, except that the type and concentration of the solute and the type and concentration of the salt having an imide anion were changed. The battery was fabricated and evaluated. In addition, all the free acid concentration in the electrolyte solution used in the Example was 50 mass ppm or less. The evaluation results are shown in Table 13. In Examples 10-1 to 10-18 and Comparative Examples 10-1 to 10-9, the values of the internal resistance characteristics and gas generation amount of the battery do not include the salt having the imide anion of the present invention. It is a relative value when the internal resistance after the cycle of the laminated cell produced using the electrolytic solution and the gas generation amount accompanying the cycle test are set to 100, respectively.

* In Examples 10-1 to 10-6 and Comparative Examples 10-1 to 10-3, relative values when the value of Comparative Example 10-1 is 100 Example 10-7 to 10-12, Comparative Example 10 -4, 10-5, relative values when the value of Comparative Example 10-4 is 100. In Examples 10-13, 10-14, and Comparative Example 10-6, the value of Comparative Example 10-6 is 100. Relative values in Examples 10-15, 10-16, and Comparative Example 10-7, relative values in Examples 10-17, 10-18, and Comparative Example 10 when the value of Comparative Example 10-7 is 100 -8, 10-9, relative value when the value of Comparative Example 10-8 is 100

From the results of Table 13, also in the sodium ion battery, the example in which the salt having the imide anion of the present invention was added to the electrolytic solution had better internal resistance characteristics and gas generation than the comparative example in which the salt was not added. The amount suppression effect was confirmed.

When the salt having an imide anion of the present invention is not included (Comparative Examples 10-1, 10-4, 10-6, 10-7, 10-8), it has an imide anion containing only a phosphorus atom or only a sulfur atom. When salt is used (Comparative Examples 10-2, 10-3, 10-5, 10-9), the internal resistance is relatively high and the amount of gas generated is also relatively large. On the other hand, when both the salt having an imide anion of the present invention and hexafluorophosphate were contained, good internal resistance characteristics and a gas generation amount suppressing effect were confirmed.

Further, in any of the examples in which other solutes and additives were added to the electrolyte solution in addition to NaPF ₆ , in the examples in which the salt having the imide anion of the present invention was added, the imide anion of the present invention was added. It was confirmed that the internal resistance characteristics and the gas generation amount suppressing effect were improved and the same effect was obtained as compared with the comparative example in which the salt was not added.

[Examples 11-1 to 11-21, Comparative Examples 11-1 to 11-19] <Experimental example 2 with other solutes and additives added>
A non-aqueous electrolyte No. 1 was prepared in the same procedure as in Example 1-1 except that the preparation conditions for the non-aqueous electrolyte shown in Table 14 were followed. D-1 to D-40 were prepared and evaluated in the same manner. Each electrolytic solution contains 1.0 mol / L of LiPF ₆ as a solute, and the concentration of the total amount of the compounds represented by the general formulas [2] to [5] in the electrolytic solution is less than 5 ppm by mass. Moreover, all the free acid concentrations in the electrolyte solution used in the examples were 120 mass ppm or less. In addition, the positive electrode body whose positive electrode active material is LiNi _0.6 Co _0.2 Mn _0.2 O ₂ is 5% by mass of 90% by mass of LiNi _0.6 Co _0.2 Mn _0.2 O ₂ powder, 5% by mass of PVDF as a binder, and 5% by mass of acetylene black as a conductive material. The mixture was mixed, further N-methylpyrrolidone was added, and the resulting paste was applied on an aluminum foil and dried. The end-of-charge voltage during battery evaluation was 4.35V, and the end-of-discharge voltage was 3.0V. The positive electrode body in which the positive electrode active material is LiNi _0.6 Co _0.2 Mn _0.2 O ₂ + LiMn ₂ O ₄ is obtained by mixing 60% by mass of LiNi _0.6 Co _0.2 Mn _0.2 O ₂ powder and 30% by mass of LiMn ₂ O ₄ powder, 5% by mass of PVDF, 5% by mass of acetylene black as a conductive material, N-methylpyrrolidone was added, and the obtained paste was applied onto an aluminum foil and dried. The end-of-charge voltage during battery evaluation was 4.2 V, and the end-of-discharge voltage was 3.0 V.
Table 15 shows the evaluation results of the batteries using the above electrolytic solution and electrodes. In addition, each value of -30 degreeC internal resistance characteristic and gas generation amount of the battery of Table 15 is internal resistance after the cycle of the lamination cell produced using the electrolyte solution which does not contain the salt which has the imide anion of this invention. , And relative values when the amount of gas generated in the cycle test is 100, respectively.

(* Examples 11-1 to 11-14 are relative values when the values of Comparative Examples 11-1 to 11-14 are set to 100, respectively.
Examples 11-15 are relative values when the value of Comparative Example 11-1 is 100,
Examples 11-16 are relative values when the value of Comparative Example 11-2 is 100,
Examples 11-17 are relative values when the value of Comparative Example 11-15 is 100,
Examples 11-18 are relative values when the value of Comparative Example 11-16 is 100,
Examples 11-19 are relative values when the value of Comparative Example 11-17 is 100,
Examples 11-20 are relative values when the value of Comparative Example 11-18 is 100,
Example 11-21 is a relative value when the value of Comparative Example 11-19 is 100)

As described above, in addition to LiPF ₆ , in addition to LiPF ₆ , other solutes and additives are further included in the electrolytic solution, and in any of the examples in which the total of lithium salts is 3 to 4 or more, the non-aqueous solution of the present invention is used. It was confirmed that the internal resistance characteristics and gas generation amount of the laminate cell using the electrolytic solution for the electrolytic solution battery were superior to the corresponding comparative examples. Therefore, by using the non-aqueous electrolyte battery electrolyte of the present invention, a non-aqueous electrolyte battery exhibiting excellent internal resistance characteristics and gas generation amount suppression effect is obtained regardless of the type of other solutes and additives. It was shown that

[Examples 12-1 to 12-6, Comparative Examples 12-1 to 12-6] <Experimental examples using different nonaqueous solvents>
Except for the basic composition of the solute and the non-aqueous solvent according to the preparation conditions shown in Table 16, non-aqueous electrolyte No. 1 was prepared in the same procedure as in Example 1-1. E-1 to E-12 were prepared and evaluated in the same manner. In addition, the density | concentration of the total amount of the compound shown by General formula [2]-[5] in each electrolyte solution is less than 5 mass ppm. Moreover, all the free acid concentrations in the electrolyte solution used in the examples were 120 mass ppm or less. Table 17 shows the evaluation results of the battery using the electrolytic solution. In addition, each value of -30 degreeC internal resistance characteristic and gas generation amount of the battery of Table 17 is internal resistance after the cycle of the lamination cell produced using the electrolyte solution which does not contain the salt which has the imide anion of this invention. , And relative values when the amount of gas generated in the cycle test is 100, respectively.

(* Examples 12-1 to 12-6 are relative values when the values of Comparative Examples 12-1 to 12-6 are set to 100)

As described above, even when different types of non-aqueous solvents are used, the internal resistance characteristics and gas generation amount of the laminate cell using the non-aqueous electrolyte battery electrolyte according to the present invention are the corresponding comparative examples. It was confirmed that it is superior to Therefore, by using the non-aqueous electrolyte battery electrolyte of the present invention, it is possible to obtain a non-aqueous electrolyte battery exhibiting excellent internal resistance characteristics and gas generation amount suppressing effect regardless of the type of non-aqueous solvent. Indicated.

Table 18 shows an electrolytic solution No. as an electrolytic solution. The result at the time of changing each positive electrode body and each negative electrode body using A-1, A-15, and A-35 is shown.

* Examples 3-1 and 3-2 are relative values when the value of Comparative Example 3-1 is 100 * Examples 1-1 and 1-15 have the value of Comparative Example 1-1 as 100 Relative value in case * Examples 5-1 and 5-2 are relative values when the value in Comparative Example 5-1 is 100 * Examples 8-1 and 8-2 are values in Comparative Example 8-1 Relative value when the value is 100 * Examples 9-1 and 9-2 are relative values when the value of Comparative Example 9-1 is 100

<Comparison of negative electrode effect>
Examples 1-1 and 1 using a negative electrode active material having a negative potential compared to Examples 3-1 and 3-2 using noble Li ₄ Ti ₅ O ₁₂ having a negative potential as the negative electrode active material -15, Examples 5-1 and 5-2 show that the non-aqueous electrolyte battery using the non-aqueous electrolyte battery electrolyte of the present invention has a negative electrode potential of 1.5 V (Li / Li ⁺ ) In a non-aqueous electrolyte battery using a negative electrode active material of less than, it was shown that better internal resistance characteristics and gas generation amount suppression effects can be obtained.

<Comparison of positive electrode effect>
Compared to Examples 8-1 and 8-2 using LiMn ₂ O ₄ having a spinel structure as the positive electrode active material and Examples 9-1 and 9-2 using LiFePO ₄ having an olivine structure, the layered structure From the results of Examples 1-1 and 1-15 using an active material having a rock salt structure, the nonaqueous electrolyte battery using the electrolyte for a nonaqueous electrolyte battery of the present invention has a layered rock salt structure. In a non-aqueous electrolyte battery using the positive electrode active material, it was shown that more excellent internal resistance characteristics and gas generation amount suppression effects can be obtained.

Claims (10)

A non-aqueous electrolyte for a non-aqueous electrolyte battery containing a non-aqueous solvent and a solute contains at least hexafluorophosphate and / or tetrafluoroborate as a solute, and contains at least one of the following general formula [1] A salt having an imide anion represented by the formula (1), but not containing a silane compound represented by the following formula [2] and an ionic complex represented by the following formulas [3] to [5]. Electrolyte for water electrolyte battery.

[1]
[In general formula [1],
R ^{1 to} R ³ are each independently a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a carbon number Is an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. A cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number It is an organic group selected from 6 to 10 aryloxy groups, and a fluorine atom, an oxygen atom or an unsaturated bond may be present in the organic group, provided that at least one of R ^{1 to} R ³ is fluorine Is an atom,
M ^{m +} is an alkali metal cation, an alkaline earth metal cation, or an onium cation,
m represents an integer having the same number as the valence of the corresponding cation. ]

Si (R ⁴ ) _a (R ⁵ ) _4-a [2]

[In general formula [2]
R ^{4 s} are groups each independently having a carbon-carbon unsaturated bond,
R ^{5 s} are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and these groups may have a fluorine atom and / or an oxygen atom,
a is an integer of 2-4. ]

[In general formula [3],
A ^{b +} is at least one selected from the group consisting of metal ions, protons and onium ions,
F is a fluorine atom,
M is at least one selected from the group consisting of a group 13 element (Al, B), a group 14 element (Si), and a group 15 element (P, As, Sb);
O is an oxygen atom,
S is a sulfur atom,
R ⁶ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms or a hetero atom or a halogen atom, and when it has 3 or more carbon atoms, it may be a branched chain or a cyclic structure. Or —N (R ⁷ ) —, wherein R ⁷ is a hydrogen atom, an alkali metal, a ring having 1 to 10 carbon atoms, or a hydrocarbon group optionally having a hetero atom or a halogen atom. In the case where the carbon number is 3 or more, R ⁷ can also take a branched chain or a cyclic structure,
Y is a carbon atom or a sulfur atom. When Y is a carbon atom, r is 1, and when Y is a sulfur atom, r is 1 or 2.
b is 1 or 2, o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 0, 1 or 2, and p is 0 In this case, a direct bond is formed between SY. ]

[In the general formula [4]
A ^{b +} is at least one selected from the group consisting of metal ions, protons and onium ions,
F is a fluorine atom,
M is at least one selected from the group consisting of a group 13 element (Al, B), a group 14 element (Si), and a group 15 element (P, As, Sb);
O is an oxygen atom,
N is a nitrogen atom,
Y is a carbon atom or a sulfur atom, q is 1 when Y is a carbon atom, q is 1 or 2 when Y is a sulfur atom,
R ⁶ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms or a hetero atom or a halogen atom, and when it has 3 or more carbon atoms, it may be a branched chain or a cyclic structure. Or —N (R ⁷ ) —, wherein R ⁷ represents a hydrogen atom, an alkali metal, a ring having 1 to 10 carbon atoms, a hetero atom or a hydrocarbon group optionally having a halogen atom. In the case where the carbon number is 3 or more, R ⁷ can also take a branched chain or a cyclic structure,
R ⁸ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a hetero atom or a halogen atom, and when it has 3 or more carbon atoms, it has a branched chain or cyclic structure Or —N (R ⁷ ) —, where R ⁷ is a hydrogen atom, an alkali metal, a ring having 1 to 10 carbon atoms, or a hydrocarbon optionally having a hetero atom or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can also take a branched chain or a cyclic structure,
b is 1 or 2, o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 0 or 1, and p is 0 , R ⁶ on both sides of R ⁶ and a carbon atom form a direct bond, and when r is 0, a direct bond is formed between MN. ]

[In general formula [5],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluoro At least one selected from (phosphonyl) imide anion,
F is a fluorine atom,
M is any one selected from the group consisting of group 13 elements (Al, B), group 14 elements (Si), and group 15 elements (P, As, Sb), O is an oxygen atom,
N is a nitrogen atom,
Y is a carbon atom or a sulfur atom, q is 1 when Y is a carbon atom, and q is 1 or 2 when Y is a sulfur atom.
X is a carbon atom or a sulfur atom, r is 1 when X is a carbon atom, and r is 1 or 2 when X is a sulfur atom.
R ⁶ represents a ring having 1 to 10 carbon atoms or a hydrocarbon group optionally having a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used. Or represents —N (R ⁷ ) —, wherein R ⁷ represents a hydrogen atom, an alkali metal, a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. In the case where the number of carbon atoms is 3 or more, R ⁷ can also take a branched chain or a cyclic structure,
R ⁹ and R ¹⁰ are each independently a hydrocarbon group which may have a ring having 1 to 10 carbon atoms or a hetero atom or a halogen atom, and in the case where the number of carbon atoms is 3 or more, a branched chain Alternatively, it may have a cyclic structure, and may have a cyclic structure defined by the following general formula [6],

c is 0 or 1; when n is 1, c is 0 (when c is 0, D does not exist); when n is 2, c is 1;
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, s is 0 or 1, and p is 0, Forming a direct bond between Y-X,
When s is 0, N (R ⁹ ) (R ¹⁰ ) and R ⁶ are directly bonded. In this case, the following structures [7] to [10] can be taken, and the direct bond is a double bond. In the case of [8] and [10], R ¹⁰ does not exist and can take a structure in which the double bond is out of the ring. In this case, R ¹¹ and R ¹² are each independently In addition, a hydrogen atom, or a hydrocarbon group which may have a ring having 1 to 10 carbon atoms or a hetero atom or a halogen atom, and when it has 3 or more carbon atoms, a branched chain or cyclic structure is also used. it can. )

A salt having an imide anion represented by the general formula [1] is:
The electrolyte solution for nonaqueous electrolyte batteries according to claim 1, wherein R ^{1 to} R ³ are all compounds that are fluorine atoms. A salt having an imide anion represented by the general formula [1] is:
At least one of R ^{1 to} R ³ is a fluorine atom;
The electrolyte solution for a non-aqueous electrolyte battery according to claim 1, wherein at least one of R ^{1 to} R ³ is a compound selected from a hydrocarbon group having 6 or less carbon atoms which may contain a fluorine atom. A salt having an imide anion represented by the general formula [1] is:
At least one of R ^{1 to} R ³ is a fluorine atom;
At least one of R ^{1 to} R ³ is a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxyl group, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a 2-propynyl group, or 2-propynyloxy. Group, phenyl group, phenyloxy group, 2,2-difluoroethyl group, 2,2-difluoroethyloxy group, 2,2,2-trifluoroethyl group, 2,2,2-trifluoroethyloxy group, 2 , 2,3,3-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyloxy group, 1,1,1,3,3,3-hexafluoroisopropyl group, and 1,1,1, The electrolyte solution for nonaqueous electrolyte batteries according to claim 1 or 3, wherein the electrolyte solution is a compound selected from 3,3,3-hexafluoroisopropyloxy groups. The counter cation of the salt having an imide anion represented by the general formula [1] is
The electrolyte solution for nonaqueous electrolyte batteries according to any one of claims 1 to 4, which is selected from the group consisting of lithium ions, sodium ions, potassium ions, and tetraalkylammonium ions. Further, as solutes, LiPF ₂ (C ₂ O ₄ ) ₂ , LiPF ₄ (C ₂ O ₄ ), LiP (C ₂ O ₄ ) ₃ , LiBF ₂ (C ₂ O ₄ ), LiB (C ₂ O ₄ ) ₂ , LiPO ₂ F ₂ , LiN (F ₂ PO) ₂ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (FSO ₂ ), LiSO ₃ F, NaPF ₂ (C ₂ O ₄ ) ₂ , NaPF ₄ (C ₂ O ₄ ), NaP (C ₂ O ₄ ) ₃ , NaBF ₂ (C ₂ O ₄ ), NaB (C ₂ O ₄ ) ₂ , NaPO ₂ F ₂ , NaN (F ₂ PO) ₂ , NaN (FSO ₂ ) ₂ , NaSO ₃ F, NaN (CF ₃ SO ₂ ) ₂ , and at least one selected from the group consisting of NaN (CF ₃ SO ₂ ) (FSO ₂ ) Item 6. The electrolyte for a non-aqueous electrolyte battery according to any one of Items 1 to 5. The amount of the salt having an imide anion represented by the general formula [1] is
With respect to the total amount of the nonaqueous solvent, the solute, and the salt having an imide anion represented by the general formula [1],
The electrolyte solution for nonaqueous electrolyte batteries according to any one of claims 1 to 6, which is in the range of 0.005 to 12.0 mass%.    Furthermore, vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, 1,6-diisocyanatohexane, ethynyl ethylene carbonate, trans-difluoroethylene carbonate, propane sultone, propene sultone, 1,3,2-dioxathiolane-2,2 Dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, 1,2-ethanedisulfonic anhydride, tris (trimethylsilyl) borate, succinonitrile, (ethoxy) penta 8. At least one additive selected from the group consisting of fluorocyclotriphosphazene, t-butylbenzene, t-amylbenzene, fluorobenzene, and cyclohexylbenzene, Nonaqueous electrolyte battery electrolyte according to any misalignment.   The non-aqueous solvent is at least one selected from the group consisting of a cyclic carbonate, a chain carbonate, a cyclic ester, a chain ester, a cyclic ether, a chain ether, a sulfone compound, a sulfoxide compound, and an ionic liquid. The electrolyte solution for nonaqueous electrolyte batteries in any one of 1-8.   A nonaqueous electrolyte battery comprising at least a positive electrode, a negative electrode, and the electrolyte for a nonaqueous electrolyte battery according to claim 1.